Going against the Grain: Atomistic Modeling of Grain Boundaries in Solid Electrolytes for Solid-State BatteriesClick to copy article linkArticle link copied!
- James A. Dawson*James A. Dawson*E-mail: [email protected]Chemistry − School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, United KingdomCentre for Energy, Newcastle University, Newcastle upon Tyne NE1 7RU, United KingdomThe Faraday Institution, Didcot OX11 0RA, United KingdomMore by James A. Dawson
Abstract
Atomistic modeling techniques, including density functional theory and molecular dynamics, play a critical role in the understanding, design, discovery, and optimization of bulk solid electrolyte materials for solid-state batteries. In contrast, despite the fact that the atomistic simulation of microstructural inhomogeneities, such as grain boundaries, can reveal essential information regarding the performance of solid electrolytes, such simulations have so far only been limited to a relatively small selection of materials. In this Perspective, the fundamental properties of grain boundaries in solid electrolytes that can be determined and manipulated through state-of-the-art atomistic modeling are illustrated through recent studies in the literature. The insights and examples presented here will inspire future computational studies of grain boundaries with the aim of overcoming their often detrimental impact on ion transport and dendrite growth inhibition in solid electrolytes.
This publication is licensed under
License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
Creative Commons (CC): This is a Creative Commons license.
Attribution (BY): Credit must be given to the creator.
*Disclaimer
This summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials.
Special Issue
Published as part of the ACS Materials Au virtual special issue “2023 Rising Stars”.
1. Introduction
Figure 1
Figure 1. Schematic illustration of the atomistic modeling of individual GBs and polycrystals.
2. Computational Methods
2.1. First-Principles Methods
2.2. Force Field-Based Methods
2.3. Atomistic Modeling of Grain Boundaries and Polycrystals
Figure 2
Figure 2. (a) Formation of a GB model where two lattices are misaligned by a tilt angle θ about a rotation axis o. An optional rigid-body translation τ of one grain relative to the other yields asymmetric GBs. The GB plane is defined by a normal vector n and distance scalar d. Atoms of each crystal are rejected based on their position relative to the GB plane. (b) Procedure for generating polycrystals where crystal “seeds” are distributed in a simulation box and randomly misoriented. Regions associated with each seed are determined using Voronoi tessellation to yield grain volumes. Each seed is expanded to populate each grain volume with atoms to yield a polycrystal.
3. Modeling Ion Transport at Grain Boundaries
Figure 3
Figure 3. (a) Calculated relative densities of Li (top panels) and mean electrostatic potentials around Li ions, ϕLi, (bottom panels) as a function of distance from the GB for the Li3OCl Σ3(112), Li3OCl Σ5(310), Li2OHCl Σ3(112), and Li2OHCl Σ5(310) GBs at 600 K. (b) Vector autocorrelation function, C(t), for OH– rotation at the bulk and GBs of Li2OHCl. Reproduced with permission under a CC BY 4.0 license from ref (18). Copyright 2023, Wiley-VCH.
Figure 4
Figure 4. (a) Li-ion trajectory densities accumulated from AIMD simulations at 1000 K in Σ1(110) and Σ3(112) LLZO GBs and bulk LLZO. Reproduced with permission from ref (72). Copyright 2022, Wiley-VCH. (b) Arrhenius plots of Li-ion diffusion coefficients in undoped and Al- and Nb-doped Σ3(112) GB models of LLZO. (c) Partial Li-ion trajectory densities accumulated from AIMD simulations at 1000 K in Al- and Nb-doped Σ3(112) GB models of LLZO. The dashed circles indicate disconnection of the trajectory density. Reproduced with permission from ref (73). Copyright 2022, Royal Chemical Society.
Figure 5
Figure 5. Diffusion density plots of Na ions (blue) overlaid on PS4 (yellow) and PO4 (red) tetrahedra in (a) Na3PS4 and (b) Na3PO4 polycrystals, respectively, with two grains at 400 K. Red circles highlight areas of significant intergranular diffusion. Reproduced with permission from ref (22). Copyright 2019, American Chemical Society.
4. Modeling Mechanical Properties and Electronic Structure at Grain Boundaries
Figure 6
Figure 6. MD-calculated elastic constants C33 and C44 at 300 K as a function of position normal to the GB planes for (a, b) a Σ5 symmetric tilt GB and (c, d) a Σ5 twist GB in LLZO. Reproduced with permission from ref (82). Copyright 2018, American Chemical Society.
Figure 7
Figure 7. (a) Calculated bandgaps of various solid electrolytes in the bulk and in the vicinity of GBs. Isosurface plots of (b) a hole polaron in Li3OCl and (c) an electron polaron in Li3InCl6. (d) Adiabatic potential energy surface associated with the hopping of each polaron. Reproduced with permission under a CC BY 4.0 license from ref (18). Copyright 2023, Wiley-VCH.
5. Conclusions and Outlook
Biography
James A. Dawson
James A. Dawson is a Reader and Newcastle University Academic Track Fellow in Energy Materials in the School of Natural and Environmental Sciences. His research utilizes state-of-the-art computational techniques to investigate ion transport and interfaces in energy materials. Before joining Newcastle University in 2020, James held postdoctoral positions at the Universities of Bath (2016–2019) and Cambridge (2015–2016), as well as a prestigious JSPS Postdoctoral Fellowship at Kyoto University (2013–2015). He completed his Ph.D. on perovskite oxides at the University of Sheffield in 2013. James has received several early career awards and was recently awarded the 2023 Harrison-Meldola Memorial Prize from the Royal Society of Chemistry.
Acknowledgments
J.A.D. gratefully acknowledges the Newcastle University Academic Track (NUAcT) Fellowship scheme, the Engineering and Physical Sciences Research Council (EPSRC, EP/V013130/1), and the Faraday Institution (FIRG026) for funding.
References
This article references 83 other publications.
- 1Grey, C. P.; Hall, D. S. Prospects for Lithium-Ion Batteries and beyond─a 2030 Vision. Nat. Commun. 2020, 11 (1), 6279, DOI: 10.1038/s41467-020-19991-4Google Scholar1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXisFemu7%252FK&md5=fa9d0069ae9b095d300a78f0cc7c444cProspects for lithium-ion batteries and beyond-a 2030 visionGrey, Clare P.; Hall, David S.Nature Communications (2020), 11 (1), 6279CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)A review. It would be unwise to assume 'conventional' lithium-ion batteries are approaching the end of their era and so we discuss current strategies to improve the current and next generation systems, where a holistic approach will be needed to unlock higher energy d. while also maintaining lifetime and safety. We end by briefly reviewing areas where fundamental science advances will be needed to enable revolutionary new battery systems.
- 2Tian, Y.; Zeng, G.; Rutt, A.; Shi, T.; Kim, H.; Wang, J.; Koettgen, J.; Sun, Y.; Ouyang, B.; Chen, T.; Lun, Z.; Rong, Z.; Persson, K.; Ceder, G. Promises and Challenges of Next-Generation “Beyond Li-Ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev. 2021, 121 (3), 1623– 1669, DOI: 10.1021/acs.chemrev.0c00767Google Scholar2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXis1Krtr3I&md5=52d967164a85b111c6f9ee02bea85e87Promises and challenges of next-generation "beyond lithium-ion" batteries for electric vehicles and grid decarbonizationTian, Yaosen; Zeng, Guobo; Rutt, Ann; Shi, Tan; Kim, Haegyeom; Wang, Jingyang; Koettgen, Julius; Sun, Yingzhi; Ouyang, Bin; Chen, Tina; Lun, Zhengyan; Rong, Ziqin; Persson, Kristin; Ceder, GerbrandChemical Reviews (Washington, DC, United States) (2021), 121 (3), 1623-1669CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. The tremendous improvement in performance and cost of lithium-ion batteries (LIBs) have made them the technol. of choice for elec. energy storage. While established battery chemistries and cell architectures for Li-ion batteries achieve good power and energy d., LIBs are unlikely to meet all the performance, cost, and scaling targets required for energy storage, in particular, in large-scale applications such as electrified transportation and grids. The demand to further reduce cost and/or increase energy d., as well as the growing concern related to natural resource needs for Li-ion have accelerated the investigation of so-called "beyond Li-ion" technologies. In this review, we will discuss the recent achievements, challenges, and opportunities of four important "beyond Li-ion" technologies: Na-ion batteries, K-ion batteries, all-solid-state batteries, and multivalent batteries. The fundamental science behind the challenges, and potential solns. toward the goals of a low-cost and/or high-energy-d. future, are discussed in detail for each technol. While it is unlikely that any given new technol. will fully replace Li-ion in the near future, "beyond Li-ion" technologies should be thought of as opportunities for energy storage to grow into mid/large-scale applications.
- 3Thackeray, M. M.; Wolverton, C.; Isaacs, E. D. Electrical Energy Storage for Transportation─Approaching the Limits of, and Going beyond, Lithium-Ion Batteries. Energy Environ. Sci. 2012, 5 (7), 7854– 7863, DOI: 10.1039/c2ee21892eGoogle Scholar3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XptVWku70%253D&md5=d681fdb77cf76bcc104bd3726dabddb8Electrical energy storage for transportation-approaching the limits of, and going beyond, lithium-ion batteriesThackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D.Energy & Environmental Science (2012), 5 (7), 7854-7863CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. The escalating and unpredictable cost of oil, the concn. of major oil resources in the hands of a few politically sensitive nations, and the long-term impact of CO2 emissions on global climate constitute a major challenge for the 21st century. They also constitute a major incentive to harness alternative sources of energy and means of vehicle propulsion. Today's lithium-ion batteries, although suitable for small-scale devices, do not yet have sufficient energy or life for use in vehicles that would match the performance of internal combustion vehicles. Energy densities 2 and 5 times greater are required to meet the performance goals of a future generation of plug-in hybrid-elec. vehicles (PHEVs) with a 40-80 mi all-elec. range, and all-elec. vehicles (EVs) with a 300-400 mi range, resp. Major advances have been made in lithium-battery technol. over the past two decades by the discovery of new materials and designs through intuitive approaches, exptl. and predictive reasoning, and meticulous control of surface structures and chem. reactions. Further improvements in energy d. of factors of two to three may yet be achievable for current day lithium-ion systems; factors of five or more may be possible for lithium-oxygen systems, ultimately leading to our ability to confine extremely high potential energy in a small vol. without compromising safety, but only if daunting technol. barriers can be overcome.
- 4Choi, J. W.; Aurbach, D. Promise and Reality of Post-Lithium-Ion Batteries with High Energy Densities. Nat. Rev. Mater. 2016, 1 (4), 16013, DOI: 10.1038/natrevmats.2016.13Google Scholar4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVert7k%253D&md5=3d2782c5ebf801e43442f01f2206379fPromise and reality of post-lithium-ion batteries with high energy densitiesChoi, Jang Wook; Aurbach, DoronNature Reviews Materials (2016), 1 (4), 16013CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Energy d. is the main property of rechargeable batteries that has driven the entire technol. forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead-acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-elec. vehicles. In this Review, we present a crit. overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technol., and also evaluate these materials under com. cell configurations.
- 5Frith, J. T.; Lacey, M. J.; Ulissi, U. A Non-Academic Perspective on the Future of Lithium-Based Batteries. Nat. Commun. 2023, 14 (1), 420, DOI: 10.1038/s41467-023-35933-2Google Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhvFCis78%253D&md5=fa41aef9f4ff4b655e62d488c4b10fc8A non-academic perspective on the future of lithium-based batteriesFrith, James T.; Lacey, Matthew J.; Ulissi, UldericoNature Communications (2023), 14 (1), 420CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Abstr.: In the field of lithium-based batteries, there is often a substantial divide between academic research and industrial market needs. This is in part driven by a lack of peer-reviewed publications from industry. Here we present a non-academic view on applied research in lithium-based batteries to sharpen the focus and help bridge the gap between academic and industrial research. We focus our discussion on key metrics and challenges to be considered when developing new technologies in this industry. We also explore the need to consider various performance aspects in unison when developing a new material/technol. Moreover, we also investigate the suitability of supply chains, sustainability of materials and the impact on system-level cost as factors that need to be accounted for when working on new technologies. With these considerations in mind, we then assess the latest developments in the lithium-based battery industry, providing our views on the challenges and prospects of various technologies.
- 6Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-3Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7I&md5=582754f689db47f9562c6f4201f150bfFundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 7Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2, 16103, DOI: 10.1038/natrevmats.2016.103Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXislGitr0%253D&md5=be4704bc600127083842361f9e75c578Lithium battery chemistries enabled by solid-state electrolytesManthiram, Arumugam; Yu, Xingwen; Wang, ShaofeiNature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
- 8Xiao, Y.; Wang, Y.; Bo, S.-H.; Kim, J. C.; Miara, L. J.; Ceder, G. Understanding Interface Stability in Solid-State Batteries. Nat. Rev. Mater. 2020, 5 (2), 105– 126, DOI: 10.1038/s41578-019-0157-5Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVert7jP&md5=7cfe14defb708589a92617809ef0b029Understanding interface stability in solid-state batteriesXiao, Yihan; Wang, Yan; Bo, Shou-Hang; Kim, Jae Chul; Miara, Lincoln J.; Ceder, GerbrandNature Reviews Materials (2020), 5 (2), 105-126CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Solid-state batteries (SSBs) using a solid electrolyte show potential for providing improved safety as well as higher energy and power d. compared with conventional Li-ion batteries. However, two crit. bottlenecks remain: the development of solid electrolytes with ionic conductivities comparable to or higher than those of conventional liq. electrolytes and the creation of stable interfaces between SSB components, including the active material, solid electrolyte and conductive additives. Although the first goal has been achieved in several solid ionic conductors, the high impedance at various solid/solid interfaces remains a challenge. Recently, computational models based on ab initio calcns. have successfully predicted the stability of solid electrolytes in various systems. In addn., a large amt. of exptl. data has been accumulated for different interfaces in SSBs. In this Review, we summarize the exptl. findings for various classes of solid electrolytes and relate them to computational predictions, with the aim of providing a deeper understanding of the interfacial reactions and insight for the future design and engineering of interfaces in SSBs. We find that, in general, the electrochem. stability and interfacial reaction products can be captured with a small set of chem. and phys. principles.
- 9Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H.-H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P.; Giordano, L.; Shao-Horn, Y. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. Chem. Rev. 2016, 116 (1), 140– 162, DOI: 10.1021/acs.chemrev.5b00563Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjtF2itA%253D%253D&md5=50c8d626d5489138b35dd462054cfa98Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion ConductionBachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis; Chang, Hao-Hsun; Pour, Nir; Lux, Simon F.; Paschos, Odysseas; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Giordano, Livia; Shao-Horn, YangChemical Reviews (Washington, DC, United States) (2016), 116 (1), 140-162CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochem. energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the cond. through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielec. consts. and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Exptl. studies and theor. results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the phys. parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors.
- 10Janek, J.; Zeier, W. G. Challenges in Speeding up Solid-State Battery Development. Nat. Energy 2023, 8 (3), 230– 240, DOI: 10.1038/s41560-023-01208-9Google ScholarThere is no corresponding record for this reference.
- 11Guo, Y.; Wu, S.; He, Y.-B.; Kang, F.; Chen, L.; Li, H.; Yang, Q.-H. Solid-State Lithium Batteries: Safety and Prospects. eScience 2022, 2 (2), 138– 163, DOI: 10.1016/j.esci.2022.02.008Google ScholarThere is no corresponding record for this reference.
- 12Bates, A. M.; Preger, Y.; Torres-Castro, L.; Harrison, K. L.; Harris, S. J.; Hewson, J. Are Solid-State Batteries Safer than Lithium-Ion Batteries?. Joule 2022, 6 (4), 742– 755, DOI: 10.1016/j.joule.2022.02.007Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhtFaqt7bJ&md5=24a4834ae6108de0381068e13ef6925cAre solid-state batteries safer than lithium-ion batteries?Bates, Alex M.; Preger, Yuliya; Torres-Castro, Loraine; Harrison, Katharine L.; Harris, Stephen J.; Hewson, JohnJoule (2022), 6 (4), 742-755CODEN: JOULBR; ISSN:2542-4351. (Cell Press)A review. All-solid-state batteries are often assumed to be safer than conventional Li-ion ones. In this work, we present the first thermodn. models to quant. evaluate solid-state and Li-ion battery heat release under several failure scenarios. The solid-state battery anal. is carried out with an Li7La3Zr2O12 solid electrolyte but can be extended to other configurations using the accompanying spreadsheet. We consider solid-state batteries that include a relatively small amt. of liq. electrolyte, which is often added at the cathode to reduce interfacial resistance. While the addn. of small amts. of liq. electrolyte increases heat release under specific failure scenarios, it may be small enough that other considerations, such as manufacturability and performance, are more important com. We show that short-circuited all-solid-state batteries can reach temps. significantly higher than conventional Li-ion, which could lead to fire through flammable packaging and/or nearby materials. Our work highlights the need for quant. safety analyses of solid-state batteries.
- 13Zhao, Q.; Stalin, S.; Zhao, C.-Z.; Archer, L. A. Designing Solid-State Electrolytes for Safe, Energy-Dense Batteries. Nat. Rev. Mater. 2020, 5 (3), 229– 252, DOI: 10.1038/s41578-019-0165-5Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtFyks74%253D&md5=d5aa2c58ad523b3289f44f0a2499892fDesigning solid-state electrolytes for safe, energy-dense batteriesZhao, Qing; Stalin, Sanjuna; Zhao, Chen-Zi; Archer, Lynden A.Nature Reviews Materials (2020), 5 (3), 229-252CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Abstr.: Solid-state electrolytes (SSEs) have emerged as high-priority materials for safe, energy-dense and reversible storage of electrochem. energy in batteries. In this Review, we assess recent progress in the design, synthesis and anal. of SSEs, and identify key failure modes, performance limitations and design concepts for creating SSEs to meet requirements for practical applications. We provide an overview of the development and characteristics of SSEs, followed by anal. of ion transport in the bulk and at interfaces based on different single-valent (Li+, Na+, K+) and multivalent (Mg2+, Zn2+, Ca2+, Al3+) cation carriers of contemporary interest. We analyze the progress in overcoming issues assocd. with the poor ionic cond. and high interfacial resistance of inorg. SSEs and the poor oxidative stability and cation transference nos. of polymer SSEs. Perspectives are provided on the design requirements for future generations of SSEs, with a focus on the chem., geometric, mech., electrochem. and interfacial transport features required to accelerate progress towards practical solid-state batteries in which metals are paired with energetic cathode chemistries, including Ni-rich and Li-rich intercalating materials, sustainable org. materials, S8, O2 and CO2.
- 14Albertus, P.; Anandan, V.; Ban, C.; Balsara, N.; Belharouak, I.; Buettner-Garrett, J.; Chen, Z.; Daniel, C.; Doeff, M.; Dudney, N. J.; Dunn, B.; Harris, S. J.; Herle, S.; Herbert, E.; Kalnaus, S.; Libera, J. A.; Lu, D.; Martin, S.; McCloskey, B. D.; McDowell, M. T.; Meng, Y. S.; Nanda, J.; Sakamoto, J.; Self, E. C.; Tepavcevic, S.; Wachsman, E.; Wang, C.; Westover, A. S.; Xiao, J.; Yersak, T. Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries. ACS Energy Lett. 2021, 1399– 1404, DOI: 10.1021/acsenergylett.1c00445Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmvVCmsLY%253D&md5=8de2940c82b1d2767d98def586dae92eChallenges for and Pathways toward Li-Metal-Based All-Solid-State BatteriesAlbertus, Paul; Anandan, Venkataramani; Ban, Chunmei; Balsara, Nitash; Belharouak, Ilias; Buettner-Garrett, Josh; Chen, Zonghai; Daniel, Claus; Doeff, Marca; Dudney, Nancy J.; Dunn, Bruce; Harris, Stephen J.; Herle, Subramanya; Herbert, Eric; Kalnaus, Sergiy; Libera, Joesph A.; Lu, Dongping; Martin, Steve; McCloskey, Bryan D.; McDowell, Matthew T.; Meng, Y. Shirley; Nanda, Jagjit; Sakamoto, Jeff; Self, Ethan C.; Tepavcevic, Sanja; Wachsman, Eric; Wang, Chunsheng; Westover, Andrew S.; Xiao, Jie; Yersak, ThomasACS Energy Letters (2021), 6 (4), 1399-1404CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Solid-state batteries hold great promise for high-energy batteries for elec. vehicles and other applications. While the potential is great, success is contingent on solving crit. challenges in materials science, processing science, and fabrication of practical full cells. This focus article has outlined several key challenges in the hope that they will encourage and inspire solns. and the eventual realization of high-energy solid-state batteries.
- 15Xia, S.; Wu, X.; Zhang, Z.; Cui, Y.; Liu, W. Practical Challenges and Future Perspectives of All-Solid-State Lithium-Metal Batteries. Chem. 2019, 5 (4), 753– 785, DOI: 10.1016/j.chempr.2018.11.013Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXnsVejsbs%253D&md5=8a74f693b991ab0ee331cd47a06ddeaePractical Challenges and Future Perspectives of All-Solid-State Lithium-Metal BatteriesXia, Shuixin; Wu, Xinsheng; Zhang, Zhichu; Cui, Yi; Liu, WeiChem (2019), 5 (4), 753-785CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)The fundamental understandings and technol. innovations in lithium-ion batteries are essential for delivering high energy d., stable cyclability, and cost-effective energy storages with the growing demands in the applications of elec. vehicles and smart grid. Solid-state electrolytes (SSEs) are more promising than org. liq. electrolyte in terms of excellent safety in developing lithium-metal anode as well as other high-capacity cathode chemistries, such as sulfur and oxygen. Considerable efforts have been made to give birth to the superionic conductors with ionic conductivities higher than 10-3 S cm-1 at room temp. However, the high interfacial impedances from the poor compatibility of SSEs with electrodes limit their practical applications, which are discussed in this review. Furthermore, the recent advances and crit. challenges for all-solid-state lithium-metal batteries based on the cathode materials of lithium-intercalation compds., sulfur, and oxygen are overviewed, and their future developments are also prospected.
- 16Ning, Z.; Li, G.; Melvin, D. L. R.; Chen, Y.; Bu, J.; Spencer-Jolly, D.; Liu, J.; Hu, B.; Gao, X.; Perera, J.; Gong, C.; Pu, S. D.; Zhang, S.; Liu, B.; Hartley, G. O.; Bodey, A. J.; Todd, R. I.; Grant, P. S.; Armstrong, D. E. J.; Marrow, T. J.; Monroe, C. W.; Bruce, P. G. Dendrite Initiation and Propagation in Lithium Metal Solid-State Batteries. Nature 2023, 618 (7964), 287– 293, DOI: 10.1038/s41586-023-05970-4Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtFOksrjJ&md5=77e737ef2df085a5ee9e5117ece77427Dendrite initiation and propagation in lithium metal solid-state batteriesNing, Ziyang; Li, Guanchen; Melvin, Dominic L. R.; Chen, Yang; Bu, Junfu; Spencer-Jolly, Dominic; Liu, Junliang; Hu, Bingkun; Gao, Xiangwen; Perera, Johann; Gong, Chen; Pu, Shengda D.; Zhang, Shengming; Liu, Boyang; Hartley, Gareth O.; Bodey, Andrew J.; Todd, Richard I.; Grant, Patrick S.; Armstrong, David E. J.; Marrow, T. James; Monroe, Charles W.; Bruce, Peter G.Nature (London, United Kingdom) (2023), 618 (7964), 287-293CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are sep. processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is detd. by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population d. and c.d., propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, c.d., stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the no. of cycles before short circuit in cells in which dendrites have initiated.
- 17Dawson, J. A.; Canepa, P.; Famprikis, T.; Masquelier, C.; Islam, M. S. Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries. J. Am. Chem. Soc. 2018, 140 (1), 362– 368, DOI: 10.1021/jacs.7b10593Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFCktLvP&md5=af5abf35aa307fc19351588fc3702227Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State BatteriesDawson, James A.; Canepa, Pieremanuele; Famprikis, Theodosios; Masquelier, Christian; Islam, M. SaifulJournal of the American Chemical Society (2018), 140 (1), 362-368CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Solid electrolytes are generating considerable interest for all-solid-state Li-ion batteries to address safety and performance issues. Grain boundaries have a significant influence on solid electrolytes and are key hurdles that must be overcome for their successful application. However, grain boundary effects on ionic transport are not fully understood, esp. at the at. scale. The Li-rich anti-perovskite Li3OCl is a promising solid electrolyte, although there is debate concerning the precise Li-ion migration barriers and cond. Using Li3OCl as a model polycryst. electrolyte, we apply large-scale mol. dynamics simulations to analyze the ionic transport at stable grain boundaries. Our results predict high concns. of grain boundaries and clearly show that Li-ion cond. is severely hindered through the grain boundaries. The activation energies for Li-ion conduction traversing the grain boundaries are consistently higher than that of the bulk crystal, confirming the high grain boundary resistance in this material. Using our results, we propose a polycryst. model to quantify the impact of grain boundaries on cond. as a function of grain size. Such insights provide valuable fundamental understanding of the role of grain boundaries and how tailoring the microstructure can lead to the optimization of new high-performance solid electrolytes.
- 18Quirk, J. A.; Dawson, J. A. Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors. Adv. Energy Mater. 2023, 13, 2301114, DOI: 10.1002/aenm.202301114Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsFaht7rP&md5=5e9a278988cba0b447fc51bbc5bf1817Design Principles for Grain Boundaries in Solid-State Lithium-Ion ConductorsQuirk, James A.; Dawson, James A.Advanced Energy Materials (2023), 13 (32), 2301114CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Lithium dendrite formation and insufficient ionic cond. remain primary concerns for the utilization of solid-state batteries. Given that the interpretation of exptl. results for polycryst. solid electrolytes can be difficult, computational techniques are invaluable for providing insight at the at. scale. Here, first-principles calcns. are carried out on representative grain boundaries in four important solid electrolytes, namely, an anti-perovskite oxide, Li3OCl, and its hydrated counterpart, Li2OHCl, a thiophosphate, Li3PS4, and a halide, Li3InCl6, to develop the first generally applicable design principles for grain boundaries in solid electrolytes for solid-state batteries. The significantly different impacts that grain boundaries have on electronic structure and transport, ion cond. and correlated ion dynamics are demonstrated. The results show that even when grain boundaries do not significantly impact ionic cond., they can still strongly perturb the electronic structure and contribute to potential lithium dendrite propagation. It is also illustrated, for the first time, how correlated motion, including the so-called paddle-wheel mechanism, can vary substantially at grain boundaries. These findings reveal the dramatically different behavior of solid electrolytes at the microscale compared to the bulk and its potential consequences and benefits for the design of solid-state batteries. These design principles are expected to aid the synthesis and engineering of solid electrolytes at the microscale for preventing dendrite propagation and accelerating ion transport.
- 19Milan, E.; Pasta, M. The Role of Grain Boundaries in Solid-State Li-Metal Batteries. Materials Futures 2023, 2 (1), 013501, DOI: 10.1088/2752-5724/aca703Google ScholarThere is no corresponding record for this reference.
- 20Zhang, Z.; Shao, Y.; Lotsch, B.; Hu, Y.-S.; Li, H.; Janek, J.; Nazar, L. F.; Nan, C.-W.; Maier, J.; Armand, M.; Chen, L. New Horizons for Inorganic Solid State Ion Conductors. Energy Environ. Sci. 2018, 11 (8), 1945– 1976, DOI: 10.1039/C8EE01053FGoogle Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFCmsLjJ&md5=446ed0fac045cbb01d3747b81e7577e9New horizons for inorganic solid state ion conductorsZhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina; Hu, Yong-Sheng; Li, Hong; Janek, Jurgen; Nazar, Linda F.; Nan, Ce-Wen; Maier, Joachim; Armand, Michel; Chen, LiquanEnergy & Environmental Science (2018), 11 (8), 1945-1976CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Among the contenders in the new generation energy storage arena, all-solid-state batteries (ASSBs) have emerged as particularly promising, owing to their potential to exhibit high safety, high energy d. and long cycle life. The relatively low cond. of most solid electrolytes and the often sluggish charge transfer kinetics at the interface between solid electrolyte and electrode layers are considered to be amongst the major challenges facing ASSBs. This review presents an overview of the state of the art in solid lithium and sodium ion conductors, with an emphasis on inorg. materials. The correlations between the compn., structure and cond. of these solid electrolytes are illustrated and strategies to boost ion cond. are proposed. In particular, the high grain boundary resistance of solid oxide electrolytes is identified as a challenge. Crit. issues of solid electrolytes beyond ion cond. are also discussed with respect to their potential problems for practical applications. The chem. and electrochem. stabilities of solid electrolytes are discussed, as are chemo-mech. effects which have been overlooked to some extent. Furthermore, strategies to improve the practical performance of ASSBs, including optimizing the interface between solid electrolytes and electrode materials to improve stability and lower charge transfer resistance are also suggested.
- 21Priester, L. Grain Boundaries: From Theory to Engineering; Springer: New York, 2013.Google ScholarThere is no corresponding record for this reference.
- 22Dawson, J. A.; Canepa, P.; Clarke, M. J.; Famprikis, T.; Ghosh, D.; Islam, M. S. Toward Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid Electrolytes. Chem. Mater. 2019, 31 (14), 5296– 5304, DOI: 10.1021/acs.chemmater.9b01794Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1CqsbvJ&md5=50b49e9fb95a443c5f40ee8e9af23d9dToward Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid ElectrolytesDawson, James A.; Canepa, Pieremanuele; Clarke, Matthew J.; Famprikis, Theodosios; Ghosh, Dibyajyoti; Islam, M. SaifulChemistry of Materials (2019), 31 (14), 5296-5304CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liq. electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic cond. is the apparently reduced grain boundary resistance of sulfide solid electrolytes compared to their oxide counterparts, but this is not fully established. Using 2 model electrolyte systems, Na3PS4 and Na3PO4, the authors apply a novel microscale simulation approach to analyze ionic transport in polycryst. materials with various grain vols. For Na3PO4, high grain boundary resistance is found, with the Na-ion cond. decreasing with decreasing grain vol. For Na3PS4, the overall influence of grain boundaries (GBs) is significantly reduced compared to the oxide. Detailed anal. reveals a minimal change in the local structures and Na-ion conduction mechanism between bulk and polycryst. Na3PS4, whereas the change is far more substantial for Na3PO4, with evidence of over-coordination of Na ions at the GBs. The microscale approach helps to explain the fundamentally different influences of GBs on ion transport in phosphate and thiophosphate solid electrolytes.
- 23Han, F.; Westover, A. S.; Yue, J.; Fan, X.; Wang, F.; Chi, M.; Leonard, D. N.; Dudney, N. J.; Wang, H.; Wang, C. High Electronic Conductivity as the Origin of Lithium Dendrite Formation within Solid Electrolytes. Nat. Energy 2019, 4 (3), 187– 196, DOI: 10.1038/s41560-018-0312-zGoogle Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmslGktbc%253D&md5=bc9f7d5bd77f27144060254fea0474f1High electronic conductivity as the origin of lithium dendrite formation within solid electrolytesHan, Fudong; Westover, Andrew S.; Yue, Jie; Fan, Xiulin; Wang, Fei; Chi, Miaofang; Leonard, Donovan N.; Dudney, Nancy J.; Wang, Howard; Wang, ChunshengNature Energy (2019), 4 (3), 187-196CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Solid electrolytes (SEs) are widely considered as an 'enabler' of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S-P2S5 is actually much easier than that in liq. electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concn. profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concn. in LiPON can be obsd., we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic cond. of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic cond., rather than further increasing the ionic cond. of SEs, is therefore crit. for the success of all-solid-state Li batteries.
- 24Liu, X.; Garcia-Mendez, R.; Lupini, A. R.; Cheng, Y.; Hood, Z. D.; Han, F.; Sharafi, A.; Idrobo, J. C.; Dudney, N. J.; Wang, C.; Ma, C.; Sakamoto, J.; Chi, M. Local Electronic Structure Variation Resulting in Li ‘Filament’ Formation within Solid Electrolytes. Nat. Mater. 2021, 20 (11), 1485– 1490, DOI: 10.1038/s41563-021-01019-xGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1WqtrjF&md5=8e49128d7024b4efac3bf42cb0bd7c51Local electronic structure variation resulting in lithium filament formation within solid electrolytesLiu, Xiaoming; Garcia-Mendez, Regina; Lupini, Andrew R.; Cheng, Yongqiang; Hood, Zachary D.; Han, Fudong; Sharafi, Asma; Idrobo, Juan Carlos; Dudney, Nancy J.; Wang, Chunsheng; Ma, Cheng; Sakamoto, Jeff; Chi, MiaofangNature Materials (2021), 20 (11), 1485-1490CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Solid electrolytes hold great promise for enabling the use of Li metal anodes. The main problem is that during cycling, Li can infiltrate along grain boundaries and cause short circuits, resulting in potentially catastrophic battery failure. At present, this phenomenon is not well understood. Here, through electron microscopy measurements on a representative system, Li7La3Zr2O12, we discover that Li infiltration in solid oxide electrolytes is strongly assocd. with local electronic band structure. About half of the Li7La3Zr2O12 grain boundaries were found to have a reduced bandgap, around 1-3 eV, making them potential channels for leakage current. Instead of combining with electrons at the cathode, Li+ ions are hence prematurely reduced by electrons at grain boundaries, forming local Li filaments. The eventual interconnection of these filaments results in a short circuit. Our discovery reveals that the grain-boundary electronic cond. must be a primary concern for optimization in future solid-state battery design.
- 25Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14 (10), 1026– 1031, DOI: 10.1038/nmat4369Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlCksb%252FI&md5=114ad3946493cf35ef3ee5d65e37c2d7Design principles for solid-state lithium superionic conductorsWang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, GerbrandNature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
- 26He, X.; Zhu, Y.; Mo, Y. Origin of Fast Ion Diffusion in Super-Ionic Conductors. Nat. Commun. 2017, 8 (May), 15893, DOI: 10.1038/ncomms15893Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVeqtbjM&md5=ca442e7d39979b975b99586daaabf1f9Origin of fast ion diffusion in super-ionic conductorsHe, Xingfeng; Zhu, Yizhou; Mo, YifeiNature Communications (2017), 8 (), 15893CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)Super-ionic conductor materials have great potential to enable novel technologies in energy storage and conversion. However, it is not yet understood why only a few materials can deliver exceptionally higher ionic cond. than typical solids or how one can design fast ion conductors following simple principles. Using ab initio modeling, here we show that fast diffusion in super-ionic conductors does not occur through isolated ion hopping as is typical in solids, but instead proceeds through concerted migrations of multiple ions with low energy barriers. Furthermore, we elucidate that the low energy barriers of the concerted ionic diffusion are a result of unique mobile ion configurations and strong mobile ion interactions in super-ionic conductors. Our results provide a general framework and universal strategy to design solid materials with fast ionic diffusion.
- 27Poletayev, A. D.; Dawson, J. A.; Islam, M. S.; Lindenberg, A. M. Defect-Driven Anomalous Transport in Fast-Ion Conducting Solid Electrolytes. Nat. Mater. 2022, 21 (9), 1066– 1073, DOI: 10.1038/s41563-022-01316-zGoogle Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFOgsLzK&md5=6afcc953f75686af1d61700bcee60022Defect-driven anomalous transport in fast-ion conducting solid electrolytesPoletayev, Andrey D.; Dawson, James A.; Islam, M. Saiful; Lindenberg, Aaron M.Nature Materials (2022), 21 (9), 1066-1073CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Solid-state ionic conduction is a key enabler of electrochem. energy storage and conversion. The mechanistic connections between material processing, defect chem., transport dynamics and practical performance are of considerable importance but remain incomplete. Here, inspired by studies of fluids and biophys. systems, we re-examine anomalous diffusion in the iconic two-dimensional fast-ion conductors, the β- and β''-aluminas. Using large-scale simulations, we reproduce the frequency dependence of alternating-current ionic cond. data. We show how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder and leads to persistent subdiffusive ion transport at macroscopic timescales. We deconvolute the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects, and geometric crowding on ionic cond. Finally, our characterization of memory effects in transport connects atomistic defect chem. to macroscopic performance with minimal assumptions and enables mechanism-driven 'atoms-to-device' optimization of fast-ion conductors.
- 28Ong, S. P.; Mo, Y.; Richards, W. D.; Miara, L.; Lee, H. S.; Ceder, G. Phase Stability, Electrochemical Stability and Ionic Conductivity of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) Family of Superionic Conductors. Energy Environ. Sci. 2013, 6 (1), 148– 156, DOI: 10.1039/C2EE23355JGoogle Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvVKqtLfM&md5=eeb3311cb7157b8e8471315d471251e9Phase stability, electrochemical stability and ionic conductivity of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductorsOng, Shyue Ping; Mo, Yifei; Richards, William Davidson; Miara, Lincoln; Lee, Hyo Sug; Ceder, GerbrandEnergy & Environmental Science (2013), 6 (1), 148-156CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We present an investigation of the phase stability, electrochem. stability and Li+ cond. of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors using first principles calcns. The Li10GeP2S12 (LGPS) superionic conductor has the highest Li+ cond. reported to date, with excellent electrochem. performance demonstrated in a Li-ion rechargeable battery. Our results show that isovalent cation substitutions of Ge4+ have a small effect on the relevant intrinsic properties, with Li10SiP2S12 and Li10SnP2S12 having similar phase stability, electrochem. stability and Li+ cond. as LGPS. Aliovalent cation substitutions (M = Al or P) with compensating changes in the Li+ concn. also have a small effect on the Li+ cond. in this structure. Anion substitutions, however, have a much larger effect on these properties. The oxygen-substituted Li10MP2O12 compds. are predicted not to be stable (with equil. decompn. energies >90 meV per atom) and have much lower Li+ conductivities than their sulfide counterparts. The selenium-substituted Li10MP2Se12 compds., on the other hand, show a marginal improvement in cond., but at the expense of reduced electrochem. stability. We also studied the effect of lattice parameter changes on the Li+ cond. and found the same asymmetry in behavior between increases and decreases in the lattice parameters, i.e., decreases in the lattice parameters lower the Li+ cond. significantly, while increases in the lattice parameters increase the Li+ cond. only marginally. Based on these results, we conclude that the size of the S2- is near optimal for Li+ conduction in this structural framework.
- 29Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28 (1), 266– 273, DOI: 10.1021/acs.chemmater.5b04082Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvFKltbrP&md5=5cfe0951cc716630f75508770bc9e1e3Interface Stability in Solid-State BatteriesRichards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, GerbrandChemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
- 30Schwietert, T. K.; Arszelewska, V. A.; Wang, C.; Yu, C.; Vasileiadis, A.; de Klerk, N. J. J.; Hageman, J.; Hupfer, T.; Kerkamm, I.; Xu, Y.; van der Maas, E.; Kelder, E. M.; Ganapathy, S.; Wagemaker, M. Clarifying the Relationship between Redox Activity and Electrochemical Stability in Solid Electrolytes. Nat. Mater. 2020, 19 (4), 428– 435, DOI: 10.1038/s41563-019-0576-0Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXpsFOruw%253D%253D&md5=75eb3965f4d23b778ec1335aad245702Clarifying the relationship between redox activity and electrochemical stability in solid electrolytesSchwietert, Tammo K.; Arszelewska, Violetta A.; Wang, Chao; Yu, Chuang; Vasileiadis, Alexandros; de Klerk, Niek J. J.; Hageman, Jart; Hupfer, Thomas; Kerkamm, Ingo; Xu, Yaolin; van der Maas, Eveline; Kelder, Erik M.; Ganapathy, Swapna; Wagemaker, MarnixNature Materials (2020), 19 (4), 428-435CODEN: NMAACR; ISSN:1476-1122. (Nature Research)All-solid-state Li-ion batteries promise safer electrochem. energy storage with larger volumetric and gravimetric energy densities. A major concern is the limited electrochem. stability of solid electrolytes and related detrimental electrochem. reactions, esp. because of our restricted understanding. Here we demonstrate for the argyrodite-, garnet- and NASICON-type solid electrolytes that the favorable decompn. pathway is indirect rather than direct, via (de)lithiated states of the solid electrolyte, into the thermodynamically stable decompn. products. The consequence is that the electrochem. stability window of the solid electrolyte is notably larger than predicted for direct decompn., rationalizing the obsd. stability window. The obsd. argyrodite metastable (de)lithiated solid electrolyte phases contribute to the (ir)reversible cycling capacity of all-solid-state batteries, in addn. to the contribution of the decompn. products, comprehensively explaining solid electrolyte redox activity. The fundamental nature of the proposed mechanism suggests this is a key aspect for solid electrolytes in general, guiding interface and material design for all-solid-state batteries.
- 31Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26 (14), 4248– 4255, DOI: 10.1021/cm5016959Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVymtLjO&md5=7f33a221907521fc8fce4b4353dcb170Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion BatteryHaruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, YoshitakaChemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
- 32Gorai, P.; Famprikis, T.; Singh, B.; Stevanović, V.; Canepa, P. Devil Is in the Defects: Electronic Conductivity in Solid Electrolytes. Chem. Mater. 2021, 33 (18), 7484– 7498, DOI: 10.1021/acs.chemmater.1c02345Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFensrnF&md5=3039fb463fef992e2b99b17a6015ed28Defects and electronic conductivity in solid electrolytesGorai, Prashun; Famprikis, Theodosios; Singh, Baltej; Stevanovic, Vladan; Canepa, PieremanueleChemistry of Materials (2021), 33 (18), 7484-7498CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Rechargeable solid-state batteries (SSBs) continue to gain prominence due to their increased safety. However, a no. of outstanding challenges still prevent their adoption in mainstream technol. This study reveals one of the origins of electronic cond., σe, in solid electrolytes (SEs), which is deemed responsible for SSB degrdn., as well as more drastic short-circuit and failure mechanisms. Using first-principles defect calcns. and physics-based models, we predict σe in three topical SEs: Li6PS5Cl and Li6PS5I argyrodites and Na3PS4 for post-Li batteries. We treat SEs as materials with finite band gaps and apply the defect theory of semiconductors to calc. the native defect concns. and assocd. electronic conductivities. Li6PS5Cl, Li6PS5I, and Na3PS4 were synthesized and characterized with UV-vis spectroscopy, which validates our computational approach confirming the occurrence of defects within the band gap of these SEs. The quant. agreement of the predicted σe in these SEs and those measured exptl. strongly suggests that doping by native defects is a major source of electronic cond. in SEs even without considering purposefully introduced dopants and/or grain boundaries. We find that Li6PS5Cl and Li6PS5I are n-type (electrons are the majority carriers), while Na3PS4 is p-type (holes). We suggest general defect engineering strategies pertaining to synthesis protocols to reduce σe in SEs and thereby curtailing the degrdn. mechanism. The methodol. presented here can be extended to est. σe in solid-electrolyte interphases. Our methodol. also provides a quant. measure of the native defects in SEs at different synthesis conditions, which is paramount to understand the effects of defects on the ionic cond.
- 33Li, Y.; Canepa, P.; Gorai, P. Role of Electronic Passivation in Stabilizing the Lithium-LixPOyNz Solid-Electrolyte Interphase. PRX Energy 2022, 1 (2), 23004, DOI: 10.1103/PRXEnergy.1.023004Google ScholarThere is no corresponding record for this reference.
- 34Squires, A. G.; Scanlon, D. O.; Morgan, B. J. Native Defects and Their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12. Chem. Mater. 2020, 32 (5), 1876– 1886, DOI: 10.1021/acs.chemmater.9b04319Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVGhtbnK&md5=d04a8d8c646be8aa5e6b1ebf122005caNative Defects and Their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12Squires, Alexander G.; Scanlon, David O.; Morgan, Benjamin J.Chemistry of Materials (2020), 32 (5), 1876-1886CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The Li-stuffed garnets LixM2M3'O12 are promising Li-ion solid electrolytes with potential use in solid-state batteries. One strategy for optimizing ionic conductivities in these materials is to tune lithium stoichiometries through aliovalent doping, which is often assumed to produce proportionate nos. of charge-compensating Li vacancies. The native defect chem. of the Li-stuffed garnets, and their response to doping, however, are not well understood, and it is unknown to what degree a simple vacancy-compensation model is valid. Here, we report hybrid d.-functional-theory calcns. of a broad range of native defects in the prototypical Li-garnet Li7La3Zr2O12 . We calc. equil. defect concns. as a function of synthesis conditions, and model the response of these defect populations to extrinsic doping. We predict a rich defect chem. that includes Li and O vacancies and interstitials, and significant nos. of cation-antisite defects. Under reducing conditions, O vacancies act as color-centers by trapping electrons. We find that supervalent (donor) doping does not produce charge compensating Li vacancies under all synthesis conditions; under Li-rich / Zr-poor conditions the dominant compensating defects are LiZr antisites, and Li stoichiometries strongly deviate from those predicted by simple "vacancy compensation" models.
- 35Zhu, F.; Islam, M. S.; Zhou, L.; Gu, Z.; Liu, T.; Wang, X.; Luo, J.; Nan, C.-W.; Mo, Y.; Ma, C. Single-Atom-Layer Traps in a Solid Electrolyte for Lithium Batteries. Nat. Commun. 2020, 11 (1), 1828, DOI: 10.1038/s41467-020-15544-xGoogle Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXntFOhsLc%253D&md5=d7fe46a3a3c292b94a78aefdf0b5c936Single-atom-layer traps in a solid electrolyte for lithium batteriesZhu, Feng; Islam, Md. Shafiqul; Zhou, Lin; Gu, Zhenqi; Liu, Ting; Wang, Xinchao; Luo, Jun; Nan, Ce-Wen; Mo, Yifei; Ma, ChengNature Communications (2020), 11 (1), 1828CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)In order to fully understand the lithium-ion transport mechanism in solid electrolytes for batteries, not only the periodic lattice but also the non-periodic features that disrupt the ideal periodicity must be comprehensively studied. At present only a limited no. of non-periodic features such as point defects and grain boundaries are considered in mechanistic studies. Here, we discover an addnl. type of non-periodic feature that significantly influences ionic transport; this feature is termed a "single-atom-layer trap" (SALT). In a prototype solid electrolyte Li0.33La0.56TiO3, the single-atom-layer defects that form closed loops, i.e., SALTs, are found ubiquitous by at.-resoln. electron microscopy. According to ab initio calcns., these defect loops prevent large vols. of materials from participating in ionic transport, and thus severely degrade the total cond. This discovery points out the urgency of thoroughly investigating different types of non-periodic features, and motivates similar studies for other solid electrolytes.
- 36Shin, D. O.; Oh, K.; Kim, K. M.; Park, K.-Y.; Lee, B.; Lee, Y.-G.; Kang, K. Synergistic Multi-Doping Effects on the Li7La3Zr2O12 Solid Electrolyte for Fast Lithium Ion Conduction. Sci. Rep 2015, 5 (1), 18053, DOI: 10.1038/srep18053Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVWqtr%252FO&md5=e4662951940735540b7426b3987d7698Synergistic multi-doping effects on the Li7La3Zr2O12 solid electrolyte for fast lithium ion conductionShin, Dong Ok; Oh, Kyungbae; Kim, Kwang Man; Park, Kyu-Young; Lee, Byungju; Lee, Young-Gi; Kang, KisukScientific Reports (2015), 5 (), 18053CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)Here, we investigate the doping effects on the lithium ion transport behavior in garnet Li7La3Zr2O12 (LLZO) from the combined exptl. and theor. approach. The concn. of Li ion vacancy generated by the inclusion of aliovalent dopants such as Al3+ plays a key role in stabilizing the cubic LLZO. However, it is found that the site preference of Al in 24d position hinders the three dimensionally connected Li ion movement when heavily doped according to the structural refinement and the DFT calcns. In this report, we demonstrate that the multi-doping using addnl. Ta dopants into the Al-doped LLZO shifts the most energetically favorable sites of Al in the crystal structure from 24d to 96 h Li site, thereby providing more open space for Li ion transport. As a result of these synergistic effects, the multi-doped LLZO shows about three times higher ionic cond. of 6.14 × 10-4 S cm-1 than that of the singly-doped LLZO with a much less efforts in stabilizing cubic phases in the synthetic condition.
- 37Zhu, Y.; Connell, J. G.; Tepavcevic, S.; Zapol, P.; Garcia-Mendez, R.; Taylor, N. J.; Sakamoto, J.; Ingram, B. J.; Curtiss, L. A.; Freeland, J. W.; Fong, D. D.; Markovic, N. M. Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal. Adv. Energy Mater. 2019, 9 (12), 1803440, DOI: 10.1002/aenm.201803440Google ScholarThere is no corresponding record for this reference.
- 38de Klerk, N. J. J.; Wagemaker, M. Diffusion Mechanism of the Sodium-Ion Solid Electrolyte Na3PS4 and Potential Improvements of Halogen Doping. Chem. Mater. 2016, 28 (9), 3122– 3130, DOI: 10.1021/acs.chemmater.6b00698Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlvV2isLg%253D&md5=9ea12d404ba117dcd2be97c3bb80c8b4Diffusion Mechanism of the Sodium-Ion Solid Electrolyte Na3PS4 and Potential Improvements of Halogen Dopingde Klerk, Niek J. J.; Wagemaker, MarnixChemistry of Materials (2016), 28 (9), 3122-3130CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)D. functional theory (DFT) mol. dynamics (MD)-simulations were performed on cubic and tetragonal Na3PS4. The MD simulations show that the Na-cond. based on the predicted self-diffusion is high in both the cubic and tetragonal phases. Higher Na-ion cond. in Na3PS4 can be obtained by introducing Na-ion vacancies. Just 2% vacancies result in a cond. of 0.2 S/cm, which is an order of magnitude larger than the calcd. cond. of the stoichiometric compd. MD simulations of halogen-doped cubic Na3PS4 suggest a practical route to introduce vacancies, where Br-doping is predicted to result in the highest bulk cond. Detailed study of the Na-ion transitions during the MD simulation reveals the role of vacancies and phonons in the diffusion mechanism. Also, the orders of magnitude difference between the MD simulations and probably macroscopic cond. can should be significantly increased by reducing the grain boundary resistance.
- 39Walsh, A.; Sokol, A. A.; Catlow, C. R. A. Computational Approaches to Energy Materials; Wiley: Chichester, 2013.Google ScholarThere is no corresponding record for this reference.
- 40Schleder, G. R.; Padilha, A. C. M.; Acosta, C. M.; Costa, M.; Fazzio, A. From DFT to Machine Learning: Recent Approaches to Materials Science-a Review. Journal of Physics: Materials 2019, 2 (3), 032001, DOI: 10.1088/2515-7639/ab084bGoogle ScholarThere is no corresponding record for this reference.
- 41Urban, A.; Seo, D.-H.; Ceder, G. Computational Understanding of Li-Ion Batteries. NPJ. Comput. Mater. 2016, 2 (1), 16002, DOI: 10.1038/npjcompumats.2016.2Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlslantL8%253D&md5=9ad3bdbb59d84c313b52507eb4f7cb0eComputational understanding of Li-ion batteriesUrban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrandnpj Computational Materials (2016), 2 (), 16002CODEN: NCMPCS; ISSN:2057-3960. (Nature Publishing Group)A review. Over the last two decades, computational methods have made tremendous advances, and today many key properties of lithium-ion batteries can be accurately predicted by first principles calcns. For this reason, computations have become a cornerstone of battery-related research by providing insight into fundamental processes that are not otherwise accessible, such as ionic diffusion mechanisms and electronic structure effects, as well as a quant. comparison with exptl. results. The aim of this review is to provide an overview of state-of-the-art ab initio approaches for the modeling of battery materials. We consider techniques for the computation of equil. cell voltages, 0-K and finite-temp. voltage profiles, ionic mobility and thermal and electrolyte stability. The strengths and weaknesses of different electronic structure methods, such as DFT+U and hybrid functionals, are discussed in the context of voltage and phase diagram predictions, and we review the merits of lattice models for the evaluation of finite-temp. thermodn. and kinetics. With such a complete set of methods at hand, first principles calcns. of ordered, cryst. solids, i.e., of most electrode materials and solid electrolytes, have become reliable and quant. However, the description of mol. materials and disordered or amorphous phases remains an important challenge. We highlight recent exciting progress in this area, esp. regarding the modeling of org. electrolytes and solid-electrolyte interfaces.
- 42Canepa, P. Pushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy Materials. ACS Materials Au 2023, 3 (2), 75– 82, DOI: 10.1021/acsmaterialsau.2c00057Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisleitLvE&md5=5dfc732c1ff8ccea73679d959e1e1b7dPushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy MaterialsCanepa, PieremanueleACS Materials Au (2023), 3 (2), 75-82CODEN: AMACGU; ISSN:2694-2461. (American Chemical Society)Simulation techniques are crucial to establish a firm link between phenomena occurring at the at. scale and macroscopic observations of functional materials. Importantly, extensive sampling of space and time scales is paramount to ensure good convergence of phys. relevant quantities to describe ion transport in energy materials. Here, a no. of simulation methods to address ion transport in energy materials are discussed, with the pros and cons of each methodol. put forward. Emphasis is given to the stochastic nature of results produced by kinetic Monte Carlo, which can adequately account for compositional disorder across multiple sublattices in solids.
- 43Huang, B.; von Rudorff, G. F.; von Lilienfeld, O. A. The Central Role of Density Functional Theory in the AI Age. Science (1979) 2023, 381 (6654), 170– 175, DOI: 10.1126/science.abn3445Google ScholarThere is no corresponding record for this reference.
- 44Kresse, G.; Furthmüller, J. Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Comput. Mater. Sci. 1996, 6, 15, DOI: 10.1016/0927-0256(96)00008-0Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XmtFWgsrk%253D&md5=779b9a71bbd32904f968e39f39946190Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis setKresse, G.; Furthmuller, J.Computational Materials Science (1996), 6 (1), 15-50CODEN: CMMSEM; ISSN:0927-0256. (Elsevier)The authors present a detailed description and comparison of algorithms for performing ab-initio quantum-mech. calcns. using pseudopotentials and a plane-wave basis set. The authors will discuss: (a) partial occupancies within the framework of the linear tetrahedron method and the finite temp. d.-functional theory, (b) iterative methods for the diagonalization of the Kohn-Sham Hamiltonian and a discussion of an efficient iterative method based on the ideas of Pulay's residual minimization, which is close to an order N2atoms scaling even for relatively large systems, (c) efficient Broyden-like and Pulay-like mixing methods for the charge d. including a new special preconditioning optimized for a plane-wave basis set, (d) conjugate gradient methods for minimizing the electronic free energy with respect to all degrees of freedom simultaneously. The authors have implemented these algorithms within a powerful package called VAMP (Vienna ab-initio mol.-dynamics package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semi-conducting surfaces, phonons in simple metals, transition metals and semiconductors) and turned out to be very reliable.
- 45Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54 (16), 11169– 11186, DOI: 10.1103/PhysRevB.54.11169Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28Xms1Whu7Y%253D&md5=9c8f6f298fe5ffe37c2589d3f970a697Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis setKresse, G.; Furthmueller, J.Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
- 46Senftle, T. P.; Hong, S.; Islam, M. M.; Kylasa, S. B.; Zheng, Y.; Shin, Y. K.; Junkermeier, C.; Engel-Herbert, R.; Janik, M. J.; Aktulga, H. M.; Verstraelen, T.; Grama, A.; van Duin, A. C. T. The ReaxFF Reactive Force-Field: Development, Applications and Future Directions. NPJ. Comput. Mater. 2016, 2 (1), 15011, DOI: 10.1038/npjcompumats.2015.11Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlslantL4%253D&md5=ee5492fa7acb1ac6bbe6cba438128c20The ReaxFF reactive force-field: development, applications and future directionsSenftle, Thomas P.; Hong, Sungwook; Islam, Md. Mahbubul; Kylasa, Sudhir B.; Zheng, Yuanxia; Shin, Yun Kyung; Junkermeier, Chad; Engel-Herbert, Roman; Janik, Michael J.; Aktulga, Hasan Metin; Verstraelen, Toon; Grama, Ananth; van Duin, Adri C. T.npj Computational Materials (2016), 2 (), 15011CODEN: NCMPCS; ISSN:2057-3960. (Nature Publishing Group)The reactive force-field (ReaxFF) interat. potential is a powerful computational tool for exploring, developing and optimizing material properties. Methods based on the principles of quantum mechanics (QM), while offering valuable theor. guidance at the electronic level, are often too computationally intense for simulations that consider the full dynamic evolution of a system. Alternatively, empirical interat. potentials that are based on classical principles require significantly fewer computational resources, which enables simulations to better describe dynamic processes over longer timeframes and on larger scales. Such methods, however, typically require a predefined connectivity between atoms, precluding simulations that involve reactive events. The ReaxFF method was developed to help bridge this gap. Approaching the gap from the classical side, ReaxFF casts the empirical interat. potential within a bond-order formalism, thus implicitly describing chem. bonding without expensive QM calcns. This article provides an overview of the development, application, and future directions of the ReaxFF method.
- 47Harrison, J. A.; Schall, J. D.; Maskey, S.; Mikulski, P. T.; Knippenberg, M. T.; Morrow, B. H. Review of Force Fields and Intermolecular Potentials Used in Atomistic Computational Materials Research. Appl. Phys. Rev. 2018, 5 (3), 031104, DOI: 10.1063/1.5020808Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsF2gurvN&md5=1b14331bd7cc33a4bf38a8481acc21c1Review of force fields and intermolecular potentials used in atomistic computational materials researchHarrison, Judith A.; Schall, J. David; Maskey, Sabina; Mikulski, Paul T.; Knippenberg, M. Todd; Morrow, Brian H.Applied Physics Reviews (2018), 5 (3), 031104/1-031104/24CODEN: APRPG5; ISSN:1931-9401. (American Institute of Physics)A review. Mol. simulation is a powerful computational tool for a broad range of applications including the examn. of materials properties and accelerating drug discovery. At the heart of mol. simulation is the analytic potential energy function. These functions span the range of complexity from very simple functions used to model generic phenomena to complex functions designed to model chem. reactions. The complexity of the math. function impacts the computational speed and is typically linked to the accuracy of the results obtained from simulations that utilize the function. One approach to improving accuracy is to simply add more parameters and addnl. complexity to the analytic function. This approach is typically used in non-reactive force fields where the functional form is not derived from quantum mech. principles. The form of other types of potentials, such as the bond-order potentials, is based on quantum mechanics and has led to varying levels of accuracy and transferability. When selecting a potential energy function for use in mol. simulations, the accuracy, transferability, and computational speed must all be considered. In this focused review, some of the more commonly used potential energy functions for mol. simulations are reviewed with an eye toward presenting their general forms, strengths, and weaknesses. (c) 2018 American Institute of Physics.
- 48Müser, M. H.; Sukhomlinov, S. V.; Pastewka, L. Interatomic Potentials: Achievements and Challenges. Adv. Phys. X 2023, 8 (1), 2093129, DOI: 10.1080/23746149.2022.2093129Google ScholarThere is no corresponding record for this reference.
- 49Pedone, A.; Malavasi, G.; Menziani, M. C.; Cormack, A. N.; Segre, U. A New Self-Consistent Empirical Interatomic Potential Model for Oxides, Silicates, and Silica-Based Glasses. J. Phys. Chem. B 2006, 110 (24), 11780– 11795, DOI: 10.1021/jp0611018Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XltVCgu7c%253D&md5=e282f713a1dda5cbb5805f60090cd9fcA New Self-Consistent Empirical Interatomic Potential Model for Oxides, Silicates, and Silica-Based GlassesPedone, Alfonso; Malavasi, Gianluca; Menziani, M. Cristina; Cormack, Alastair N.; Segre, UldericoJournal of Physical Chemistry B (2006), 110 (24), 11780-11795CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)A new empirical pairwise potential model for ionic and semi-ionic oxides has been developed. Its transferability and reliability have been demonstrated by testing the potentials toward the prediction of structural and mech. properties of a wide range of silicates of technol. and geol. importance. The partial ionic charge model with a Morse function is used, and it allows the modeling of the quenching of melts, silicate glasses, and inorg. crystals at high-pressure and high-temp. conditions. The results obtained by mol. dynamics and free energy calcns. are discussed in relation to the prediction of structural and mech. properties of a series of soda lime silicate glasses.
- 50Jalem, R.; Rushton, M. J. D.; Manalastas, W.; Nakayama, M.; Kasuga, T.; Kilner, J. A.; Grimes, R. W. Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid Electrolytes. Chem. Mater. 2015, 27 (8), 2821– 2831, DOI: 10.1021/cm5045122Google Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXlvV2itLw%253D&md5=f01c2f4d22f12f5e87917b82a4ce3f59Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid ElectrolytesJalem, Randy; Rushton, M. J. D.; Manalastas, William; Nakayama, Masanobu; Kasuga, Toshihiro; Kilner, John A.; Grimes, Robin W.Chemistry of Materials (2015), 27 (8), 2821-2831CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Garnet-type Li7La3Zr2O12 (LLZrO) is a candidate solid electrolyte material that is now being intensively optimized for application in com. competitive solid state Li+ ion batteries. In this study we investigate, by force-field-based simulations, the effects of Ga3+ doping in LLZrO. We confirm the stabilizing effect of Ga3+ on the cubic phase. We also det. that Ga3+ addn. does not lead to any appreciable structural distortion. Li site connectivity is not significantly deteriorated by the Ga3+ addn. (>90% connectivity retained up to x = 0.30 in Li7-3xGaxLa3Zr2O12). Interestingly, two compositional regions are predicted for bulk Li+ ion cond. in the cubic phase: (i) a decreasing trend for 0 ≤ x ≤ 0.10 and (ii) a relatively flat trend for 0.10 < x ≤ 0.30. This cond. behavior is explained by combining analyses using percolation theory, van Hove space time correlation, the radial distribution function, and trajectory d.
- 51Kim, J.-S.; Jung, W. D.; Son, J.-W.; Lee, J.-H.; Kim, B.-K.; Chung, K.-Y.; Jung, H.-G.; Kim, H. Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium Thiophosphates. ACS Appl. Mater. Interfaces 2019, 11 (1), 13– 18, DOI: 10.1021/acsami.8b17524Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFyrsr%252FP&md5=8521e7817fa4fc157cb5700dcfba1bf3Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium ThiophosphatesKim, Ji-Su; Jung, Wo Dum; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Chung, Kyung-Yoon; Jung, Hun-Gi; Kim, HyoungchulACS Applied Materials & Interfaces (2019), 11 (1), 13-18CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The authors detd. the interat. potentials of the Li-[PS43-] building block in (Li2S)0.75(P2S5)0.25 (LPS) and predicted the Li-ion cond. (σLi) of glass-ceramic LPS from mol. dynamics. The Li-ion conduction characteristics in the cryst./interfacial/glassy structure were decompd. by considering the structural ordering differences. The superior σLi of the glassy LPS could be attributed to the fact that ∼40% of its structure consists of the short-ranged cubic S-sublattice instead of the hcp. γ-phase. This glassy LPS has a σLi of 4.08 × 10-1 mS/cm, an improvement of ∼100 times relative to that of the γ-phase, which is in agreement with the expts.
- 52Dawson, J. A.; Islam, M. S. A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li10GeP2S12 Solid Electrolyte. ACS Mater. Lett. 2022, 4 (2), 424– 431, DOI: 10.1021/acsmaterialslett.1c00766Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFSltLk%253D&md5=f12633443acbe9935f46a5f07d943641A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li10GeP2S12 Solid ElectrolyteDawson, James A.; Islam, M. SaifulACS Materials Letters (2022), 4 (2), 424-431CODEN: AMLCEF; ISSN:2639-4979. (American Chemical Society)The discovery of the lithium superionic conductor Li10GeP2S12 (LGPS) has led to significant research activity on solid electrolytes for high-performance solid-state batteries. Despite LGPS exhibiting a remarkably high room-temp. Li-ion cond., comparable to that of the liq. electrolytes used in current Li-ion batteries, nanoscale effects in this material have not been fully explored. Here, we predict that nanosizing of LGPS can be used to further enhance its Li-ion cond. By utilizing state-of-the-art nanoscale modeling techniques, our results reveal significant nanosizing effects with the Li-ion cond. of LGPS increasing with decreasing particle vol. These features are due to a fundamental change from a primarily one-dimensional Li-ion conduction mechanism to a three-dimensional mechanism and major changes in the local structure. For the smallest nanometric particle size, the Li-ion cond. at room temp. is three times higher than that of the bulk system. These findings reveal that nanosizing LGPS and related solid electrolytes could be an effective design approach to enhance their Li-ion cond.
- 53Kim, K.; Dive, A.; Grieder, A.; Adelstein, N.; Kang, S.; Wan, L. F.; Wood, B. C. Flexible Machine-Learning Interatomic Potential for Simulating Structural Disordering Behavior of Li7La3Zr2O12 Solid Electrolytes. J. Chem. Phys. 2022, 156 (22), 221101, DOI: 10.1063/5.0090341Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhsFektbnI&md5=0a496d54e76df8902bb3b22463813ad5Flexible machine-learning interatomic potential for simulating structural disordering behavior of Li7La3Zr2O12 solid electrolytesKim, Kwangnam; Dive, Aniruddha; Grieder, Andrew; Adelstein, Nicole; Kang, ShinYoung; Wan, Liwen F.; Wood, Brandon C.Journal of Chemical Physics (2022), 156 (22), 221101CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)Batteries based on solid-state electrolytes, including Li7La3Zr2O12 (LLZO), promise improved safety and increased energy d.; however, at. disorder at grain boundaries and phase boundaries can severely deteriorate their performance. Machine-learning (ML) interat. potentials offer a uniquely compelling soln. for simulating chem. processes, rare events, and phase transitions assocd. with these complex interfaces by mixing high scalability with quantum-level accuracy, provided that they can be trained to properly address at. disorder. To this end, we report the construction and validation of an ML potential that is specifically designed to simulate cryst., disordered, and amorphous LLZO systems across a wide range of conditions. The ML model is based on a neural network algorithm and is trained using ab initio data. Performance tests prove that the developed ML potential can predict accurate structural and vibrational characteristics, elastic properties, and Li diffusivity of LLZO comparable to ab initio simulations. As a demonstration of its applicability to larger systems, we show that the potential can correctly capture grain boundary effects on diffusivity, as well as the thermal transition behavior of LLZO. These examples show that the ML potential enables simulations of transitions between well-defined and disordered structures with quantum-level accuracy at speeds thousands of times faster than ab initio methods. (c) 2022 American Institute of Physics.
- 54Lee, T.; Qi, J.; Gadre, C. A.; Huyan, H.; Ko, S.-T.; Zuo, Y.; Du, C.; Li, J.; Aoki, T.; Wu, R.; Luo, J.; Ong, S. P.; Pan, X. Atomic-Scale Origin of the Low Grain-Boundary Resistance in Perovskite Solid Electrolyte Li0.375Sr0.4375Ta0.75Zr0.25O3. Nat. Commun. 2023, 14 (1), 1940, DOI: 10.1038/s41467-023-37115-6Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXnt1Gjt7o%253D&md5=f3d5e45e57b160135f0570bf855ce40fAtomic-scale origin of the low grain-boundary resistance in perovskite solid electrolyte Li0.375Sr0.4375Ta0.75Zr0.25O3Lee, Tom; Qi, Ji; Gadre, Chaitanya A.; Huyan, Huaixun; Ko, Shu-Ting; Zuo, Yunxing; Du, Chaojie; Li, Jie; Aoki, Toshihiro; Wu, Ruqian; Luo, Jian; Ong, Shyue Ping; Pan, XiaoqingNature Communications (2023), 14 (1), 1940CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Oxide solid electrolytes (OSEs) have the potential to achieve improved safety and energy d. for lithium-ion batteries, but their high grain-boundary (GB) resistance generally is a bottleneck. In the well-studied perovskite oxide solid electrolyte, Li3xLa2/3-xTiO3 (LLTO), the ionic cond. of grain boundaries is about three orders of magnitude lower than that of the bulk. In contrast, the related Li0.375Sr0.4375Ta0.75Zr0.25O3 (LSTZ0.75) perovskite exhibits low grain boundary resistance for reasons yet unknown. Here, we use aberration-cor. scanning transmission electron microscopy and spectroscopy, along with an active learning moment tensor potential, to reveal the at. scale structure and compn. of LSTZ0.75 grain boundaries. Vibrational electron energy loss spectroscopy is applied for the first time to reveal atomically resolved vibrations at grain boundaries of LSTZ0.75 and to characterize the otherwise unmeasurable Li distribution therein. We find that Li depletion, which is a major reason for the low grain boundary ionic cond. of LLTO, is absent for the grain boundaries of LSTZ0.75. Instead, the low grain boundary resistivity of LSTZ0.75 is attributed to the formation of a nanoscale defective cubic perovskite interfacial structure that contained abundant vacancies. Our study provides new insights into the at. scale mechanisms of low grain boundary resistivity.
- 55Krenzer, G.; Klarbring, J.; Tolborg, K.; Rossignol, H.; McCluskey, A. R.; Morgan, B. J.; Walsh, A. Nature of the Superionic Phase Transition of Lithium Nitride from Machine Learning Force Fields. Chem. Mater. 2023, 35 (15), 6133– 6140, DOI: 10.1021/acs.chemmater.3c01271Google Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsV2ltbnO&md5=7d6ce15d243dab3a98c9db3e76e07945Nature of the Superionic Phase Transition of Lithium Nitride from Machine Learning Force FieldsKrenzer, Gabriel; Klarbring, Johan; Tolborg, Kasper; Rossignol, Hugo; McCluskey, Andrew R.; Morgan, Benjamin J.; Walsh, AronChemistry of Materials (2023), 35 (15), 6133-6140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Superionic conductors have great potential as solid-state electrolytes, but the physics of type-II superionic transitions remains elusive. In this study, we employed mol. dynamics simulations, using machine learning force fields, to investigate the type-II superionic phase transition in α-Li3N. We characterized Li3N above and below the superionic phase transition by calcg. the heat capacity, Li+ ion self-diffusion coeff., and Li defect concns. as functions of temp. Our findings indicate that both the Li+ self-diffusion coeff. and Li vacancy concn. follow distinct Arrhenius relationships in the normal and superionic regimes. The activation energies for self-diffusion and Li vacancy formation decrease by a similar proportion across the superionic phase transition. This result suggests that the superionic transition may be driven by a decrease in defect formation energetics rather than changes in Li transport mechanism. This insight may have implications for other type-II superionic materials.
- 56Mueller, T.; Hernandez, A.; Wang, C. Machine Learning for Interatomic Potential Models. J. Chem. Phys. 2020, 152 (5), 050902, DOI: 10.1063/1.5126336Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXisV2gurY%253D&md5=a9a8b282be7a0356715e8aab2e207347Machine learning for interatomic potential modelsMueller, Tim; Hernandez, Alberto; Wang, ChuhongJournal of Chemical Physics (2020), 152 (5), 050902CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A review. The use of supervised machine learning to develop fast and accurate interat. potential models is transforming mol. and materials research by greatly accelerating at.-scale simulations with little loss of accuracy. Three years ago, Jorg Behler published a perspective in this journal providing an overview of some of the leading methods in this field. In this perspective, we provide an updated discussion of recent developments, emerging trends, and promising areas for future research in this field. We include in this discussion an overview of three emerging approaches to developing machine-learned interat. potential models that have not been extensively discussed in existing reviews: moment tensor potentials, message-passing networks, and symbolic regression. (c) 2020 American Institute of Physics.
- 57Unke, O. T.; Chmiela, S.; Sauceda, H. E.; Gastegger, M.; Poltavsky, I.; Schütt, K. T.; Tkatchenko, A.; Müller, K.-R. Machine Learning Force Fields. Chem. Rev. 2021, 121 (16), 10142– 10186, DOI: 10.1021/acs.chemrev.0c01111Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmtVOksL0%253D&md5=8a40dd8c5c642c22f40628f2b1ba22e9Machine Learning Force FieldsUnke, Oliver T.; Chmiela, Stefan; Sauceda, Huziel E.; Gastegger, Michael; Poltavsky, Igor; Schuett, Kristof T.; Tkatchenko, Alexandre; Mueller, Klaus-RobertChemical Reviews (Washington, DC, United States) (2021), 121 (16), 10142-10186CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. In recent years, the use of machine learning (ML) in computational chem. has enabled numerous advances previously out of reach due to the computational complexity of traditional electronic-structure methods. One of the most promising applications is the construction of ML-based force fields (FFs), with the aim to narrow the gap between the accuracy of ab initio methods and the efficiency of classical FFs. The key idea is to learn the statistical relation between chem. structure and potential energy without relying on a preconceived notion of fixed chem. bonds or knowledge about the relevant interactions. Such universal ML approxns. are in principle only limited by the quality and quantity of the ref. data used to train them. This review gives an overview of applications of ML-FFs and the chem. insights that can be obtained from them. The core concepts underlying ML-FFs are described in detail, and a step-by-step guide for constructing and testing them from scratch is given. The text concludes with a discussion of the challenges that remain to be overcome by the next generation of ML-FFs.
- 58Zuo, Y.; Chen, C.; Li, X.; Deng, Z.; Chen, Y.; Behler, J.; Csányi, G.; Shapeev, A. V.; Thompson, A. P.; Wood, M. A.; Ong, S. P. Performance and Cost Assessment of Machine Learning Interatomic Potentials. J. Phys. Chem. A 2020, 124 (4), 731– 745, DOI: 10.1021/acs.jpca.9b08723Google Scholar58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmtVKjsg%253D%253D&md5=7716fe55d3269109bfc101fdfc25d823Performance and Cost Assessment of Machine Learning Interatomic PotentialsZuo, Yunxing; Chen, Chi; Li, Xiangguo; Deng, Zhi; Chen, Yiming; Behler, Jorg; Csanyi, Gabor; Shapeev, Alexander V.; Thompson, Aidan P.; Wood, Mitchell A.; Ong, Shyue PingJournal of Physical Chemistry A (2020), 124 (4), 731-745CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Machine learning of the quant. relationship between local environment descriptors and the potential energy surface of a system of atoms has emerged as a new frontier in the development of interat. potentials (IAPs). Here, we present a comprehensive evaluation of machine learning IAPs (ML-IAPs) based on four local environment descriptors-atom-centered symmetry functions (ACSF), smooth overlap of at. positions (SOAP), the spectral neighbor anal. potential (SNAP) bispectrum components, and moment tensors-using a diverse data set generated using high-throughput d. functional theory (DFT) calcns. The data set comprising bcc (Li, Mo) and fcc (Cu, Ni) metals and diamond group IV semiconductors (Si, Ge) is chosen to span a range of crystal structures and bonding. All descriptors studied show excellent performance in predicting energies and forces far surpassing that of classical IAPs, as well as predicting properties such as elastic consts. and phonon dispersion curves. We observe a general trade-off between accuracy and the degrees of freedom of each model and, consequently, computational cost. We will discuss these trade-offs in the context of model selection for mol. dynamics and other applications.
- 59Thompson, A. P.; Aktulga, H. M.; Berger, R.; Bolintineanu, D. S.; Brown, W. M.; Crozier, P. S.; in ’t Veld, P. J.; Kohlmeyer, A.; Moore, S. G.; Nguyen, T. D.; Shan, R.; Stevens, M. J.; Tranchida, J.; Trott, C.; Plimpton, S. J. LAMMPS - a Flexible Simulation Tool for Particle-Based Materials Modeling at the Atomic, Meso, and Continuum Scales. Comput. Phys. Commun. 2022, 271, 108171, DOI: 10.1016/j.cpc.2021.108171Google Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlSrsb7O&md5=cd0bfd050820e97c11779003add20ed3LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scalesThompson, Aidan P.; Aktulga, H. Metin; Berger, Richard; Bolintineanu, Dan S.; Brown, W. Michael; Crozier, Paul S.; in 't Veld, Pieter J.; Kohlmeyer, Axel; Moore, Stan G.; Nguyen, Trung Dac; Shan, Ray; Stevens, Mark J.; Tranchida, Julien; Trott, Christian; Plimpton, Steven J.Computer Physics Communications (2022), 271 (), 108171CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)Since the classical mol. dynamics simulator LAMMPS was released as an open source code in 2004, it has become a widely-used tool for particle-based modeling of materials at length scales ranging from at. to mesoscale to continuum. Reasons for its popularity are that it provides a wide variety of particle interaction models for different materials, that it runs on any platform from a single CPU core to the largest supercomputers with accelerators, and that it gives users control over simulation details, either via the input script or by adding code for new interat. potentials, constraints, diagnostics, or other features needed for their models. As a result, hundreds of people have contributed new capabilities to LAMMPS and it has grown from fifty thousand lines of code in 2004 to a million lines today. In this paper several of the fundamental algorithms used in LAMMPS are described along with the design strategies which have made it flexible for both users and developers. We also highlight some capabilities recently added to the code which were enabled by this flexibility, including dynamic load balancing, on-the-fly visualization, magnetic spin dynamics models, and quantum-accuracy machine learning interat. potentials.Program Title: Large-scale Atomic/Mol. Massively Parallel Simulator (LAMMPS)CPC Library link to program files:https://doi.org/10.17632/cxbxs9btsv.1Developer's repository link:https://github.com/lammps/lammpsLicensing provisions: GPLv2Programming language: C++, Python, C, FortranSupplementary material:https://www.lammps.orgNature of problem: Many science applications in physics, chem., materials science, and related fields require parallel, scalable, and efficient generation of long, stable classical particle dynamics trajectories. Within this common problem definition, there lies a great diversity of use cases, distinguished by different particle interaction models, external constraints, as well as timescales and lengthscales ranging from at. to mesoscale to macroscopic.Soln. method: The LAMMPS code uses parallel spatial decompn., distributed neighbor lists, and parallel FFTs for long-range Coulombic interactions [1]. The time integration algorithm is based on the Stormer-Verlet symplectic integrator [2], which provides better stability than higher-order non-symplectic methods. In addn., LAMMPS supports a wide range of interat. potentials, constraints, diagnostics, software interfaces, and pre- and post-processing features.Addnl. comments including restrictions and unusual features: This paper serves as the definitive ref. for the LAMMPS code.S. Plimpton, Fast parallel algorithms for short-range mol. dynamics. Phys. 117 (1995) 1-19.L. Verlet, Computer expts. on classical fluids: I. Thermodynamical properties of Lennard-Jones mols., Phys. Rev. 159 (1967) 98-103.
- 60Hirel, P. Atomsk: A Tool for Manipulating and Converting Atomic Data Files. Comput. Phys. Commun. 2015, 197, 212– 219, DOI: 10.1016/j.cpc.2015.07.012Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlSlt7rP&md5=7869db03e79a37285988e2db890a9ce1Atomsk: A tool for manipulating and converting atomic data filesHirel, PierreComputer Physics Communications (2015), 197 (), 212-219CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)We present a libre, Open Source command-line program named Atomsk, that aims at creating and manipulating at. systems for the purposes of ab initio calcns., classical atomistic calcns., and visualization, in the areas of computational physics and chem. The program can run on GNU/Linux, Apple Mac OS X, and Microsoft Windows platforms. Many file formats are supported, allowing for easy conversion of at. configuration files. The command-line options allow to construct supercells, insert point defects (vacancies, interstitials), line defects (dislocations, cracks), plane defects (stacking faults), as well as other transformations. Several options can be applied consecutively, allowing for a comprehensive workflow from a unit cell to the final at. system. Some modes allow to construct complex structures, or to perform specific anal. of at. systems.
- 61Yu, S.; Siegel, D. J. Grain Boundary Contributions to Li-Ion Transport in the Solid Electrolyte Li7La3Zr2O12 (LLZO). Chem. Mater. 2017, 29 (22), 9639– 9647, DOI: 10.1021/acs.chemmater.7b02805Google Scholar61https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslSisbvO&md5=5546c0f2ab692c15abbe0ad785445b76Grain Boundary Contributions to Li-Ion Transport in the Solid Electrolyte Li7La3Zr2O12 (LLZO)Yu, Seungho; Siegel, Donald J.Chemistry of Materials (2017), 29 (22), 9639-9647CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The oxide with nominal compn. Li7La3Zr2O12 (LLZO) is a promising solid electrolyte thanks to its high (bulk) Li-ion cond., negligible electronic transport, chem. stability against Li metal, and wide electrochem. window. Despite these promising characteristics, recent measurements suggest that microstructural features, specifically, grain boundaries (GBs), contribute to undesirable short-circuiting and resistance in polycryst. LLZO membranes. Toward the goal of understanding GB-related phenomena, the present study characterizes the energetics, compn., and transport properties of three low-energy (S3 and S5) sym. tilt GBs in LLZO at the at. scale. Monte Carlo simulations reveal that the GB planes are enriched with Li, and to a lesser extent with oxygen. Mol. dynamics simulations on these off-stoichiometric boundaries were used to assess Li-ion transport within and across the boundary planes. We find that Li transport is generally reduced in the GB region; however, the magnitude of this effect is sensitive to temp. and GB structure. Li-ion diffusion is comparable in all three GBs at the high temps. encountered during processing, and only 2-3 times slower than bulk diffusion. These similarities vanish at room temp., where diffusion in the more compact S3 boundary remains relatively fast (half the bulk rate), while transport in the S5 boundaries is roughly 2 orders of magnitude slower. These trends mirror the activation energies for diffusion, which in the S5 boundaries are up to 35% larger than in bulk LLZO, and are identical to the bulk in the S3 boundary. Diffusion within the S5 boundaries is obsd. to be isotropic. In contrast, intraplane diffusion in the S3 boundary plane at room temp. is predicted to exceed that of the bulk, while transboundary diffusion is ∼200 times slower than that in the bulk. Our observation of mixed GB transport contributions (some boundaries support fast diffusion, while others are slow) is consistent with the limited GB resistance obsd. in polycryst. LLZO samples processed at high temps. These data also suggest that higher-energy GBs with less-compact structures should penalize Li-ion cond. to a greater degree.
- 62Chen, B.; Xu, C.; Zhou, J. Insights into Grain Boundary in Lithium-Rich Anti-Perovskite as Solid Electrolytes. J. Electrochem. Soc. 2018, 165 (16), A3946– A3951, DOI: 10.1149/2.0831816jesGoogle Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjs1emsbc%253D&md5=1a5902b2f9485e7167bccf1fda185812Insights into grain boundary in lithium-rich anti-perovskite as solid electrolytesChen, Bingbing; Xu, Chaoqun; Zhou, JianqiuJournal of the Electrochemical Society (2018), 165 (16), A3946-A3951CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)In all-solid-state Li batteries, antiperovskite solid electrolyte has high ionic cond. and high stability with Li metal anode. However, grain boundaries (GBs) contribute to undesirable resistance limiting ionic cond. in antiperovskite, and there is limited knowledge about the GBs in solid electrolyte, particularly at the at. scale. Here, using d. functional theory calcns. 4 sym tilt (Σ3 and Σ5) GBs effects on structural characteristics and ions transport in antiperovskite (Li3OCl) solid electrolyte. Using 1st-principles simulation, GBs are relatively stable resulting in its high concns. in Li3OCl. The presence of GBs can improve compatibility with electrode, while it decreases the ionic cond. and band gaps in Li3OCl. Also, the Σ5 GBs structures are softer and higher ionic cond. than Σ3 GBs, delivering a new insight that GBs types may importantly affect the softness and ionic cond. in solid electrolyte. Significantly, the easiest Li ion migration pathway is along GB direction in Li3OCl with GBs structures. The present work uncovers the GBs behaviors in antiperovskite solid electrolyte, which can help one to guide the design of high performance antiperovskite solid electrolyte.
- 63Lee, H. J.; Darminto, B.; Narayanan, S.; Diaz-Lopez, M.; Xiao, A. W.; Chart, Y.; Lee, J. H.; Dawson, J. A.; Pasta, M. Li-Ion Conductivity in Li2OHCl1-xBrx Solid Electrolytes: Grains, Grain Boundaries and Interfaces. J. Mater. Chem. A 2022, 10 (21), 11574– 11586, DOI: 10.1039/D2TA01462AGoogle Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1Cltb7L&md5=6182880e89321977415bf61e1dc3b89cLi-ion conductivity in Li2OHCl1-xBrx solid electrolytes: grains, grain boundaries and interfacesLee, Hyeon Jeong; Darminto, Brigita; Narayanan, Sudarshan; Diaz-Lopez, Maria; Xiao, Albert W.; Chart, Yvonne; Lee, Ji Hoon; Dawson, James A.; Pasta, MauroJournal of Materials Chemistry A: Materials for Energy and Sustainability (2022), 10 (21), 11574-11586CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)In this study, we conduct a comprehensive investigation of the effect of grain, grain boundary and interfacial resistance on the total Li-ion cond. in Li2OHCl1-xBrx antiperovskite solid electrolytes. We highlight how the thermal expansion coeff. can serve as an indicator for the presence of structural defects, which are difficult to probe directly with X-ray techniques, and their effect on bulk Li-ion conduction. The detrimental effect of grain boundaries on ionic cond. is investigated by atomistic calcns. and validated exptl. by electrochem. impedance spectroscopy on pellets with controlled grain size. The effect of compn. on interfacial resistance is probed by electrochem. impedance spectroscopy and XPS. These insights provide design principles to improve Li-ion cond. in lithium hydroxide halide antiperovskites.
- 64Van Duong, L.; Nguyen, M. T.; Zulueta, Y. A. Unravelling the Alkali Transport Properties in Nanocrystalline A3OX (A = Li, Na, X = Cl, Br) Solid State Electrolytes. A Theoretical Prediction. RSC Adv. 2022, 12 (31), 20029– 20036, DOI: 10.1039/D2RA03370DGoogle Scholar64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhslGgur3L&md5=c9ebf92bdaa71571c5c39f48d19b795dUnravelling the alkali transport properties in nanocrystalline A3OX (A = Li, Na, X = Cl, Br) solid state electrolytes. A theoretical predictionVan Duong, Long; Nguyen, Minh Tho; Zulueta, Yohandys A.RSC Advances (2022), 12 (31), 20029-20036CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Transport properties of the halogeno-alkali oxides A3OX (A = Li, Na, X = Cl, Br) nanocryst. samples with the presence of .sum.3(111) grain boundaries were computed using large-scale mol. dynamic simulations. Results on the diffusion/conduction process show that these nanocryst. samples are characterized with higher activation energies as compared to previous theor. studies, but closer to expt. Such a performance can be attributed to the larger at. d. at the .sum.3(111) grain boundary regions within the nanocrystals. Despite a minor deterioration of transport properties of the mixed cation Li2NaOX and Na2LiOX samples, these halogeno-alkali oxides can also be considered as good inorg. solid electrolytes in both Li- and Na-ion batteries.
- 65Dawson, J. A.; Famprikis, T.; Johnston, K. E. Anti-Perovskites for Solid-State Batteries: Recent Developments, Current Challenges and Future Prospects. J. Mater. Chem. A Mater. 2021, 9 (35), 18746– 18772, DOI: 10.1039/D1TA03680GGoogle Scholar65https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVylur%252FK&md5=f2f94c55a221b143804268510b7d865aAnti-perovskites for solid-state batteries: recent developments, current challenges and future prospectsDawson, James A.; Famprikis, Theodosios; Johnston, Karen E.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (35), 18746-18772CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A review. Current com. batteries cannot meet the requirements of next-generation technologies, meaning that the creation of new high-performance batteries at low cost is essential for the electrification of transport and large-scale energy storage. Solid-state batteries are being widely anticipated to lead to a step improvement in the performance and safety of batteries and their success is heavily dependent on the discovery, design and optimization of the solid electrolytes that they are based on. In recent years, Li- and Na-rich anti-perovskite solid electrolytes have risen to become highly promising candidate materials for solid-state batteries on the basis of their high ionic cond., wide electrochem. window, stability, low cost and structural diversity. This perspective highlights exptl. and atomistic modeling progress currently being made for Li- and Na-rich anti-perovskite solid electrolytes. We focus on several crit. areas of interest in these materials, including synthesisability, structure, ion transport mechanisms, anion rotation, interfaces and their compatibility with anti-perovskite cathodes for the possible formation of anti-perovskite electrolyte- and cathode-based solid-state batteries. The opportunities and challenges for the design and utilization of these materials in state-of-the-art solid-state batteries are also discussed. As featured throughout this perspective, the versatility, diversity and performance of anti-perovskite solid electrolytes make them one of the most important materials families currently under consideration for solid-state batteries.
- 66Dawson, J. A.; Attari, T. S.; Chen, H.; Emge, S. P.; Johnston, K. E.; Islam, M. S. Elucidating Lithium-Ion and Proton Dynamics in Anti-Perovskite Solid Electrolytes. Energy Environ. Sci. 2018, 11 (10), 2993– 3002, DOI: 10.1039/C8EE00779AGoogle Scholar66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVSqs7bP&md5=1a9ea4bb0f4d83f74082c1130d605bb7Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytesDawson, James A.; Attari, Tavleen S.; Chen, Hungru; Emge, Steffen P.; Johnston, Karen E.; Islam, M. SaifulEnergy & Environmental Science (2018), 11 (10), 2993-3002CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy d. and safety when compared to conventional liq. electrolyte-based devices. The Li-rich anti-perovskite Li3-xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of compn. are not fully characterized. In this work, we apply a combination of ab initio mol. dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3-xOHxCl. Our calcns. predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesizing moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temp. solid-state NMR expts., which indicate localized proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3-xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.
- 67Sun, Y.; Wang, Y.; Liang, X.; Xia, Y.; Peng, L.; Jia, H.; Li, H.; Bai, L.; Feng, J.; Jiang, H.; Xie, J. Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4. J. Am. Chem. Soc. 2019, 141 (14), 5640– 5644, DOI: 10.1021/jacs.9b01746Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtVCjsLY%253D&md5=48a2071f7a7637168bf6fff2598abb63Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4Sun, Yulong; Wang, Yuechao; Liang, Xinmiao; Xia, Yuanhua; Peng, Linfeng; Jia, Huanhuan; Li, Hanxiao; Bai, Liangfei; Feng, Jiwen; Jiang, Hong; Xie, JiaJournal of the American Chemical Society (2019), 141 (14), 5640-5644CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Sodium superionic conductors are keys to develop high safety and low cost all-solid-state sodium batteries. Among developed sodium ionic conductors, antiperovskite-type ionic conductors have attracted vast interest due to their high structural tolerance and good formability. Herein, Na3OBH4 with cubic antiperovskite structure is successfully synthesized by solid-state reaction from Na2O and NaBH4. Na3OBH4 exhibits ionic cond. of 4.4 × 10-3 S cm-1 at room temp. (1.1 × 10-2 S cm-1 at 328 K) and activation energy of 0.25 eV. The ionic cond. is 4 orders of magnitude higher than the existing antiperovskite Na3OX (X = Cl, Br, I). It is shown that such enhancement is not only due to the specific cubic antiperovskite structure of Na3OBH4 but also because of the rotation of BH4 cluster anion. This work deepens the understanding of the antiperovskite structure and the role of cluster anions for superionic conduction.
- 68Zhang, Z.; Nazar, L. F. Exploiting the Paddle-Wheel Mechanism for the Design of Fast Ion Conductors. Nat. Rev. Mater. 2022, 7 (5), 389– 405, DOI: 10.1038/s41578-021-00401-0Google ScholarThere is no corresponding record for this reference.
- 69Smith, J. G.; Siegel, D. J. Low-Temperature Paddlewheel Effect in Glassy Solid Electrolytes. Nat. Commun. 2020, 11 (1), 1483, DOI: 10.1038/s41467-020-15245-5Google Scholar69https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlvFGjsrs%253D&md5=fb9975d74289f6b6de944f42f824c5faLow-temperature paddlewheel effect in glassy solid electrolytesSmith, Jeffrey G.; Siegel, Donald J.Nature Communications (2020), 11 (1), 1483CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic cond. remain poorly understood. Here, ab initio mol. dynamics is used to characterize migration processes in the prototype glass, 75Li2S-25P2S5. Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS43- anions. This latter effect, known as the 'paddlewheel' mechanism, is typically obsd. in high-temp. cryst. polymorphs. In contrast to the behavior of cryst. materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temp. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable cryst. analog, γ-Li3PS4, where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses contg. complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temp. Consequently, these systems may be fertile ground in the search for new solid electrolytes.
- 70Forrester, F. N.; Quirk, J. A.; Famprikis, T.; Dawson, J. A. Disentangling Cation and Anion Dynamics in Li3PS4 Solid Electrolytes. Chem. Mater. 2022, 34 (23), 10561– 10571, DOI: 10.1021/acs.chemmater.2c02637Google Scholar70https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVajur3E&md5=bfeb37bc4d9663d92346342208fdf759Disentangling Cation and Anion Dynamics in Li3PS4 Solid ElectrolytesForrester, Frazer N.; Quirk, James A.; Famprikis, Theodosios; Dawson, James A.Chemistry of Materials (2022), 34 (23), 10561-10571CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)A prerequisite for the realization of solid-state batteries is the development of highly conductive solid electrolytes. Li3PS4 is the archetypal member of the highly promising thiophosphate family of Li-ion conductors. Despite a multitude of investigations into this material, the underlying at.-scale features governing the roles of and the relationships between cation and anion dynamics, in its various temp.-dependent polymorphs, are yet to be fully resolved. On this basis, we provide a comprehensive mol. dynamics study to probe the fundamental mechanisms underpinning fast Li-ion diffusion in this important solid electrolyte material. We first det. the Li-ion diffusion coeffs. and corresponding activation energies in the temp.-dependent γ, β, and α polymorphs of Li3PS4 and relate them to the structural and chem. characteristics of each polymorph. The roles that both cation correlation and anion libration play in enhancing the Li-ion dynamics in Li3PS4 are then isolated and revealed. For γ- and β-Li3PS4, our simulations confirm that the interat. Li-Li interaction is pivotal in detg. (and restricting) their Li-ion diffusion. For α-Li3PS4, we quantify the significant role of Li-Li correlation and anion dynamics in dominating Li-ion transport in this polymorph for the first time. The fundamental understanding and anal. presented herein is expected to be highly applicable to other solid electrolytes where the interplay between cation and anion dynamics is crucial to enhancing ion transport.
- 71Shiiba, H.; Zettsu, N.; Yamashita, M.; Onodera, H.; Jalem, R.; Nakayama, M.; Teshima, K. Molecular Dynamics Studies on the Lithium Ion Conduction Behaviors Depending on Tilted Grain Boundaries with Various Symmetries in Garnet-Type Li7La3Zr2O12. J. Phys. Chem. C 2018, 122 (38), 21755– 21762, DOI: 10.1021/acs.jpcc.8b06275Google Scholar71https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFOlt7%252FO&md5=539c0d6045737cf43e17c7a69b8bf831Molecular Dynamics Studies on the Lithium Ion Conduction Behaviors Depending on Tilted Grain Boundaries with Various Symmetries in Garnet-Type Li7La3Zr2O12Shiiba, Hiromasa; Zettsu, Nobuyuki; Yamashita, Miho; Onodera, Hitoshi; Jalem, Randy; Nakayama, Masanobu; Teshima, KatsuyaJournal of Physical Chemistry C (2018), 122 (38), 21755-21762CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Grain boundary (GB) structure is a crit. parameter that significantly affects the macroscopic properties of materials; however, the evaluation of GB characteristics by modern anal. methods remains an extremely challenging task. Li+ cond. degrdn. at the GBs of cubic Li7La3Zr2O12 (LLZO) with a garnet framework (which represents the most promising candidate material for solid electrolytes used in all-solid-state batteries) was studied by various mol. dynamics approaches combined with newly developed anal. techniques. The transboundary diffusion of Li ions was generally slower than their diffusion in the bulk regardless of the GB symmetry; however, this effect strongly depended on the concn. of Li-deficient sites (trapping Li vacancies) in the GB layer. Also, the compactness and d. of the combined GB regions represent the key parameters affecting the overall Li+ cond. of polycryst. LLZO films.
- 72Gao, B.; Jalem, R.; Tian, H.-K.; Tateyama, Y. Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte. Adv. Energy Mater. 2022, 12 (3), 2102151, DOI: 10.1002/aenm.202102151Google Scholar72https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXis12lu7jL&md5=a9fd48dd2f10160e7563a7ed3f08fbecRevealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid ElectrolyteGao, Bo; Jalem, Randy; Tian, Hong-Kang; Tateyama, YoshitakaAdvanced Energy Materials (2022), 12 (3), 2102151CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)For real applications of all-solid-state batteries (ASSBs) to be realized, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the at.-scale defect stabilities and transport of ions around GBs is still far from understood. Here, a first-principles investigation on the promising garnet Li7La3Zr2O12 (LLZO) solid electrolyte (SE) GBs is carried out. The study reveals a GB-dependent behavior for the Li-ion transport correlated to the diffusion network. Of particular note, the Σ3(112) tilt GB model exhibits a quite high Li-ion cond. comparable to that in bulk, and a fast intergranular diffusion, contrary to former discovered. Moreover, the uncovered preferential electron localization at the Σ3(112) GB leads to an increase in the electronic cond. at the GB, and the Li accumulation at the coarse GBs is revealed from the neg. Li interstitial formation energies. These factors play important roles in the dendrite formation along the GBs during Li plating in the LLZO|Li cell. These findings suggest strategies for the optimization of synthesis conditions and coating materials at the interface for preventing dendrite formation. The present comprehensive simulations provide new insights into the GB effect and engineering of the SE in ASSBs.
- 73Gao, B.; Jalem, R.; Tateyama, Y. Atomistic Insight into the Dopant Impacts at the Garnet Li7La3Zr2O12 Solid Electrolyte Grain Boundaries. J. Mater. Chem. A 2022, 10 (18), 10083– 10091, DOI: 10.1039/D2TA00545JGoogle Scholar73https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xpt1Gjsbo%253D&md5=d9d830cda74c20bd654c369fa177b156Atomistic insight into the dopant impacts at the garnet Li7La3Zr2O12 solid electrolyte grain boundariesGao, Bo; Jalem, Randy; Tateyama, YoshitakaJournal of Materials Chemistry A: Materials for Energy and Sustainability (2022), 10 (18), 10083-10091CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The garnet-type Li7La3Zr2O12 (LLZO) as one of the most promising solid electrolytes (SEs) has attracted great research attention owing to its high compatibility with Li metal anodes. Doping with a supervalent cation is an effective strategy to stabilize cubic LLZO with desired high ion cond. The behavior of dopants at the grain boundary (GB) (e.g. segregation) is expected to have a great influence on the properties of LLZO but is far from understood. Here we have performed first-principles calcns. to reveal the at.-scale impact of dopants at the GB of the LLZO SE. The results show that Al and Ga dopants at the GB are preferentially segregated at the 24d site of Li with three neighboring Li-ions, and Nb and Ta dopants prefer to locate at the 5-coordinated and partially distorted 6-coordinated Zr sites at the GB. The segregation of a Nb-like dopant at the GB will improve Li-ion cond., while the GB with an Al-like dopant shows cond. comparable to that of the undoped one and fragmentation of the Li-ion diffusion network. Moreover, the electronic state calcns. indicate electron accumulation at the doped GBs, in contrast to the mitigation effect of the dopants on dendrite formation along LLZO GBs revealed by the calcn. of Li interstitial formation energy. We also explored the potentially existing phases at the doped coarse GBs, and a series of products have been proposed. These comprehensive calcns. provide valuable atomistic insights into the dopants at the GB in the LLZO SE and substantial knowledge of optimization of this material.
- 74Cui, J.; Meng, L.; Jiang, S.; Wang, K.; Qian, J.; Wang, X. Lithium-Ion Diffusion in the Grain Boundary of Polycrystalline Solid Electrolyte Li6.75La3Zr1.5Ta0.5O12 (LLZTO): A Computer Simulation and Theoretical Study. Phys. Chem. Chem. Phys. 2022, 24 (44), 27355– 27361, DOI: 10.1039/D2CP02766FGoogle Scholar74https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVSjsLrO&md5=33baa88271e2466c714e5e1014528d6fLithium-ion diffusion in the grain boundary of polycrystalline solid electrolyte Li6.75La3Zr1.5Ta0.5O12Cui, Jiahao; Meng, Lingchen; Jiang, Shan; Wang, Kangping; Qian, Jingyu; Wang, XiyangPhysical Chemistry Chemical Physics (2022), 24 (44), 27355-27361CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Lithium-ion diffusion ability in solid electrolytes is crucial for the performance and safety of lithium-ion batteries. However, the lithium-ion diffusion coeff. of Li6.75La3Zr1.5Ta0.5O12 (LLZTO) measured exptl. is much lower than that simulated theor. because LLZTO exists widely in the polycryst. form rather than in the single-crystal form. Herein, we focus on the construction of grain boundaries in polycryst. materials to address this key issue. An amorphous structure is created by randomly throwing atoms into a virtual box, where the chem. bonds are broken and rearranged through continuous heating and annealing operations, resulting in a stable framework structure. The lithium-ion diffusion coeffs. of polycryst. LLZTO and single-crystal LLZTO calcd. via Ab initio mol. dynamics (AIMD) are consistent with the exptl. data in trend. Furthermore, the anal. of the grain boundary composed of the secondary phase in polycryst. LLZTO reveals that the continuous -O-M-O- metal oxide grid with low formation energy per atom restricts the lithium-ion migration. The lithium-ion migration barriers calcd. utilizing d. functional theory (DFT) also demonstrate the obstacle of the grain boundary from another perspective.
- 75Symington, A. R.; Molinari, M.; Dawson, J. A.; Statham, J. M.; Purton, J.; Canepa, P.; Parker, S. C. Elucidating the Nature of Grain Boundary Resistance in Lithium Lanthanum Titanate. J. Mater. Chem. A 2021, 9 (10), 6487– 6498, DOI: 10.1039/D0TA11539HGoogle Scholar75https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXjtVGjtLs%253D&md5=4512a6cce991c0533745daf969467267Elucidating the nature of grain boundary resistance in lithium lanthanum titanateSymington, Adam R.; Molinari, Marco; Dawson, James A.; Statham, Joel M.; Purton, John; Canepa, Pieremanuele; Parker, Stephen C.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (10), 6487-6498CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid electrolytes for all-solid-state batteries are generating remarkable research interest as a means to improve the safety, stability and performance of rechargeable batteries. Solid electrolytes are often polycryst. and the effect that grain boundaries have on the material properties is often not fully characterised. Here, we present a comprehensive mol. dynamics study that quantifies the effect of grain boundaries on Li-ion transport in perovskite Li3xLa(2/3)-xTiO3 (0 < x < 0.16) (LLTO). Our results predict that grain boundaries hinder Li-ion cond. by 1 to 2 orders of magnitude compared to the bulk. We attribute the poor Li-ion cond. of the grain boundaries to significant structural alterations at the grain boundaries. Our detailed anal. provides important insight into the influence of grain boundary structure on transport of Li-ions in solid electrolyte materials.
- 76Nakano, K.; Tanibata, N.; Takeda, H.; Kobayashi, R.; Nakayama, M.; Watanabe, N. Molecular Dynamics Simulation of Li-Ion Conduction at Grain Boundaries in NASICON-Type LiZr2(PO4)3 Solid Electrolytes. J. Phys. Chem. C 2021, 125 (43), 23604– 23612, DOI: 10.1021/acs.jpcc.1c07314Google Scholar76https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlSjsLrO&md5=a1ecd83324695bb61dbb09286fae5a6fMolecular Dynamics Simulation of Li-Ion Conduction at Grain Boundaries in NASICON-Type LiZr2(PO4)3 Solid ElectrolytesNakano, Koki; Tanibata, Naoto; Takeda, Hayami; Kobayashi, Ryo; Nakayama, Masanobu; Watanabe, NaokiJournal of Physical Chemistry C (2021), 125 (43), 23604-23612CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Na superionic conductor-type LiZr2(PO4)3 (LZP)-related materials are considered promising solid electrolytes that can assist in realizing rechargeable all-solid-state Li-ion batteries with high Li-ion cond. and electrochem. stability. However, the grain boundary (GB) resistance considerably reduces the total Li-ion cond. of the sintered polycryst. body, which is obsd. in LZP and several other Li-ion conductive oxides. In this regard, the rational design of solid-solid interfaces is known to improve the ionic cond. Therefore, examg. the ion conduction mechanism at GBs is important from the viewpoints of practical usability and elucidation of the fundamental knowledge on dynamics in cryst. solids. In this study, 32 GB models were constructed, consisting of various Miller indexes and terminations, and the corresponding GB Li-ion conductivities were evaluated using mol. dynamics simulations with d. functional theory-derived force-field parameters. A few of the GB models exhibited improved Li-ion conductivities compared to the bulk ionic cond. Machine learning anal. using descriptors derived from interfacial structure characteristics suggested that the size of cavities around the original Li 6b sites significantly affected the GB ionic cond., which could enable the rational design of GB structures.
- 77Kobayashi, R.; Nakano, K.; Nakayama, M. Non-Equilibrium Molecular Dynamics Study on Atomistic Origin of Grain Boundary Resistivity in NASICON-Type Li-Ion Conductor. Acta Mater. 2022, 226, 117596, DOI: 10.1016/j.actamat.2021.117596Google Scholar77https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XmsFaksA%253D%253D&md5=bcafbf6bea38bd45c562de74626a11d3Non-equilibrium molecular dynamics study on atomistic origin of grain boundary resistivity in NASICON-type Li-ion conductorKobayashi, Ryo; Nakano, Koki; Nakayama, MasanobuActa Materialia (2022), 226 (), 117596CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)Grain boundary (GB) resistance to ion conduction in solid-state electrolytes is one of the main issues on next-generation, high-performance rechargeable batteries. Thus, it is required to understand the origin of the GB resistance from the atomistic point of view. In this paper, a method to investigate the local ion flux using the non-equil. mol. dynamics (NEMD) is proposed, and it is demonstrated that the atomistic origin of the GB resistance in NASICON-type LiZr2(PO4)3 is clarified by the local ion-flux anal. of poly-cryst. system contg. over half-million atoms in combination with Li-ion site potential energy anal. The local ion-flux anal. enables us to visualize where Li ions migrate fast or slow in poly-cryst. structures, and it is obsd., for the first time, that Li ions move toward lower reaches within grains and pass through specific regions of GBs. The Li-ion site potential energy anal. provides at.-level details of the differences between high-flux and low-flux regions. It is confirmed from the analyses that the GB resistance comes from deep Li-ion traps and high-energy Li-ion migration paths made of rings of PO4 and ZrO6 polyhedra that do not exist in the cryst. structure.
- 78Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4. J. Am. Chem. Soc. 2013, 135 (3), 975– 978, DOI: 10.1021/ja3110895Google Scholar78https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXms1Ogtg%253D%253D&md5=831a6eeeff0d028622bc5808d5afd3a5Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, ChengduJournal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
- 79Shen, K.; He, R.; Wang, Y.; Zhao, C.; Chen, H. Atomistic Insights into the Role of Grain Boundary in Ionic Conductivity of Polycrystalline Solid-State Electrolytes. J. Phys. Chem. C 2020, 124 (48), 26241– 26248, DOI: 10.1021/acs.jpcc.0c07328Google Scholar79https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitlKrs73I&md5=6433429643f724c054f047321d952361Atomistic Insights into the Role of Grain Boundary in Ionic Conductivity of Polycrystalline Solid-State ElectrolytesShen, Kun; He, Ruibin; Wang, Yixuan; Zhao, Changchun; Chen, HaoJournal of Physical Chemistry C (2020), 124 (48), 26241-26248CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)It is widely accepted that grain boundary (GB) in polycryst. solid-state electrolytes (SSEs) can substantially reduce ionic conduction, which is regarded as the most essential property for SSEs. However, the phys. origin of the GB-induced retardation effects remains unanswered. In this study, mol. dynamics simulations and first-principle calcns. were combined to reveal the role of GBs in ionic conduction via the evaluation of the thermodn.-kinetic interaction between GBs and vacancy in cubic Na3PS4. Our results suggest that the reduced ionic conduction in GBs is attributed to the segregation of Na vacancy in the GB core. The GB-blocking effects strongly depend on both vacancy segregation energy and the no. of segregation sites in the GB core, which are detd. by the GB structure. This study will shed new light on the future design of polycryst. SSEs with a high ionic cond. via grain boundary engineering.
- 80Wang, Y.; Li, G.; Shen, K.; Tian, E. The Effect of Grain Boundary on Na Ion Transport in Polycrystalline Solid-State Electrolyte Cubic Na3PS4. Mater. Res. Express 2021, 8 (2), 025508, DOI: 10.1088/2053-1591/abe7b1Google Scholar80https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXntlals7k%253D&md5=77de402f771819d9707ed2c4a40672c5The effect of grain boundary on Na ion transport in polycrystalline solid-state electrolyte cubic Na3PS4Wang, Yixuan; Li, Gengwei; Shen, Kun; Tian, EnkeMaterials Research Express (2021), 8 (2), 025508CODEN: MREAC3; ISSN:2053-1591. (IOP Publishing Ltd.)In the polycryst. solid-state electrolytes (SSEs), ionic transport is directly linked to the properties of all solid-state batteries. Grain boundaries (GBs), as essential defects in SSE, were found to play a significant role in the overall kinetics of Na ion transport, while the mechanism is not well understood due to the complex role of GBs. In this study, the first principles and phase field calcns. are combined to explore the diffusion path and the interaction between point defects and grain boundaries in cubic Na3PS4 at different scales. The effects of point defects segregation on the overall kinetics of ionic transport were discussed in detail. By comparing the energy barriers required for ion transition along GBs and across GBs, the effect of the grain boundary on ionic diffusion can be influenced by local at. coordination. This study could help improve the fundamental understanding of ionic transport in polycryst. solid-state electrolytes, and provide guidance for designing new solid-state electrolytes with excellent ionic cond.
- 81Monroe, C.; Newman, J. The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces. J. Electrochem. Soc. 2005, 152 (2), A396, DOI: 10.1149/1.1850854Google Scholar81https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhs1KktLc%253D&md5=e878820c6a811396757bd7435bdb40adThe impact of elastic deformation on deposition kinetics at lithium/polymer interfacesMonroe, Charles; Newman, JohnJournal of the Electrochemical Society (2005), 152 (2), A396-A404CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Past theories of electrode stability assume that the surface tension resists the amplification of surface roughness at cathodes and show that instability at lithium/liq. interfaces cannot be prevented by surface forces alone. This work treats interfacial stability in lithium/polymer systems where the electrolyte is solid. Linear elasticity theory is employed to compute the addnl. effect of bulk mech. forces on electrode stability. The lithium and polymer are treated as Hookean elastic materials, characterized by their shear moduli and Poisson's ratios. Two-dimensional displacement distributions that satisfy force balances across a periodically deforming interface are derived; these allow computation of the stress and surface-tension forces. The incorporation of elastic effects into a kinetic model demonstrates regimes of electrolyte mech. properties where amplification of surface roughness can be inhibited. For a polymer material with Poisson's ratio similar to poly(ethylene oxide), interfacial roughening is mech. suppressed when the separator shear modulus is about twice that of lithium.
- 82Yu, S.; Siegel, D. J. Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10 (44), 38151– 38158, DOI: 10.1021/acsami.8b17223Google Scholar82https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFSrtrvK&md5=a4bc1fab4aac1040157f1c12c4e0c44aGrain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid ElectrolytesYu, Seungho; Siegel, Donald J.ACS Applied Materials & Interfaces (2018), 10 (44), 38151-38158CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Models based on linear elasticity suggest that a solid electrolyte with a high shear modulus will suppress dendrite formation in batteries that use metallic lithium as the neg. electrode. Nevertheless, recent expts. find that lithium can penetrate stiff solid electrolytes through microstructural features, such as grain boundaries. This failure mode emerges even in cases where the electrolyte has an av. shear modulus that is an order of magnitude larger than that of Li. Adopting the solid-electrolyte Li7La3Zr2O12 (LLZO) as a prototype, significant softening in elastic properties occurs in nanoscale regions near grain boundaries. Mol. dynamics simulations performed on tilt and twist boundaries reveal that the grain boundary shear modulus is up to 50% smaller than in bulk regions. Probably inhomogeneities in elastic properties arising from microstructural features provide a mechanism by which soft lithium can penetrate ostensibly stiff solid electrolytes.
- 83Kim, H.; Conlin, P.; Bergschneider, M.; Chung, H.; Kim, S. Y.; Cha, S. W.; Cho, M.; Cho, K. First Principles Study on Li Metallic Phase Nucleation at Grain Boundaries in a Lithium Lanthanum Titanium Oxide (LLTO) Solid Electrolyte. J. Mater. Chem. A 2023, 11 (6), 2889– 2898, DOI: 10.1039/D2TA07950JGoogle Scholar83https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhs1Siu7o%253D&md5=87dc35b963776572cb05bb17d0b2dae5First principles study on Li metallic phase nucleation at grain boundaries in a lithium lanthanum titanium oxide (LLTO) solid electrolyteKim, Hyungjun; Conlin, Patrick; Bergschneider, Matthew; Chung, Hayoung; Kim, Sung Youb; Cha, Suk Won; Cho, Maenghyo; Cho, KyeongjaeJournal of Materials Chemistry A: Materials for Energy and Sustainability (2023), 11 (6), 2889-2898CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid electrolytes (SEs) are crit. for next-generation all solid-state batteries with high energy d. and fire safety. However, recent studies obsd. that the Li metallic phase nucleates at the electrode interfaces as well as the interfaces between cryst. grains of SEs. Many studies have revealed the origins and control methods for Li metallic phase formation at the anode interface, but a thorough understanding of metallic Li formation at intergranular regions in SEs has not been developed yet. Through systematic DFT simulations, we present a thorough atomistic study that reveals the impact of intergranular regions on Li-metallic phase formation in SEs using the perovskite Li3xLa(2/3)-x.box.(1/3)-2xTiO3 (0 < x < 0.167) (LLTO) as a model SE. We investigated the three representative model structures for intergranular regions, which are exptl. obsd. with various microstructure configurations: (i) stoichiometric grain boundary (GB), (ii) A-site deficient GB, and (iii) intergranular pore space. In the stoichiometric GB, the GB region has an electron insulating feature regardless of A-site compns. (0 < x < 0.167). In the A-site deficient GB, however, the GB region has electronic cond., but it has a high repulsive force against Li-ions moving into the GB region. However, in the intergranular pore structure, Li-ions prefer to move with a neutral charge state into the pore space which shows a p-type conductive property. Accordingly, Li metallic phase nucleation starts in the intergranular pore space of the SE. These results elucidate the crit. role of pore space in SEs for Li metallic phase nucleation and provide an insight into the design of Li metallic phase-free SEs and further studies on SE materials.
Cited By
Smart citations by scite.ai include citation statements extracted from the full text of the citing article. The number of the statements may be higher than the number of citations provided by ACS Publications if one paper cites another multiple times or lower if scite has not yet processed some of the citing articles.
This article is cited by 6 publications.
- Ana C. C. Dutra, James A. Quirk, Ying Zhou, James A. Dawson. Influence of Surfaces on Ion Transport and Stability in Antiperovskite Solid Electrolytes at the Atomic Scale. ACS Materials Letters 2024, 6
(11)
, 5039-5047. https://doi.org/10.1021/acsmaterialslett.4c01777
- Yuxi Chen, Dongyue Liang, Elizabeth M. Y. Lee, Sokseiha Muy, Maxime Guillaume, Marc-David Braida, Antoine A. Emery, Nicola Marzari, Juan J. de Pablo. Ion Transport at Polymer–Argyrodite Interfaces. ACS Applied Materials & Interfaces 2024, 16
(36)
, 48223-48234. https://doi.org/10.1021/acsami.4c07440
- Jiale Ma, Zhenyu Li. Computational Design of Inorganic Solid-State Electrolyte Materials for Lithium-Ion Batteries. Accounts of Materials Research 2024, 5
(5)
, 523-532. https://doi.org/10.1021/accountsmr.3c00223
- Mingwei Wu, Zheng Wei, Yan Zhao, Qiu He. Recent Applications of Theoretical Calculations and Artificial Intelligence in Solid-State Electrolyte Research: A Review. Nanomaterials 2025, 15
(3)
, 225. https://doi.org/10.3390/nano15030225
- Lirong Xia, Hengzhi Liu, Yong Pei. Theoretical calculations and simulations power the design of inorganic solid-state electrolytes. Nanoscale 2024, 16
(33)
, 15481-15501. https://doi.org/10.1039/D4NR02114B
- Weihang Xie, Zeyu Deng, Zhengyu Liu, Theodosios Famprikis, Keith T. Butler, Pieremanuele Canepa. Effects of Grain Boundaries and Surfaces on Electronic and Mechanical Properties of Solid Electrolytes. Advanced Energy Materials 2024, 14
(17)
https://doi.org/10.1002/aenm.202304230
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.
Recommended Articles
Abstract
Figure 1
Figure 1. Schematic illustration of the atomistic modeling of individual GBs and polycrystals.
Figure 2
Figure 2. (a) Formation of a GB model where two lattices are misaligned by a tilt angle θ about a rotation axis o. An optional rigid-body translation τ of one grain relative to the other yields asymmetric GBs. The GB plane is defined by a normal vector n and distance scalar d. Atoms of each crystal are rejected based on their position relative to the GB plane. (b) Procedure for generating polycrystals where crystal “seeds” are distributed in a simulation box and randomly misoriented. Regions associated with each seed are determined using Voronoi tessellation to yield grain volumes. Each seed is expanded to populate each grain volume with atoms to yield a polycrystal.
Figure 3
Figure 3. (a) Calculated relative densities of Li (top panels) and mean electrostatic potentials around Li ions, ϕLi, (bottom panels) as a function of distance from the GB for the Li3OCl Σ3(112), Li3OCl Σ5(310), Li2OHCl Σ3(112), and Li2OHCl Σ5(310) GBs at 600 K. (b) Vector autocorrelation function, C(t), for OH– rotation at the bulk and GBs of Li2OHCl. Reproduced with permission under a CC BY 4.0 license from ref (18). Copyright 2023, Wiley-VCH.
Figure 4
Figure 4. (a) Li-ion trajectory densities accumulated from AIMD simulations at 1000 K in Σ1(110) and Σ3(112) LLZO GBs and bulk LLZO. Reproduced with permission from ref (72). Copyright 2022, Wiley-VCH. (b) Arrhenius plots of Li-ion diffusion coefficients in undoped and Al- and Nb-doped Σ3(112) GB models of LLZO. (c) Partial Li-ion trajectory densities accumulated from AIMD simulations at 1000 K in Al- and Nb-doped Σ3(112) GB models of LLZO. The dashed circles indicate disconnection of the trajectory density. Reproduced with permission from ref (73). Copyright 2022, Royal Chemical Society.
Figure 5
Figure 5. Diffusion density plots of Na ions (blue) overlaid on PS4 (yellow) and PO4 (red) tetrahedra in (a) Na3PS4 and (b) Na3PO4 polycrystals, respectively, with two grains at 400 K. Red circles highlight areas of significant intergranular diffusion. Reproduced with permission from ref (22). Copyright 2019, American Chemical Society.
Figure 6
Figure 6. MD-calculated elastic constants C33 and C44 at 300 K as a function of position normal to the GB planes for (a, b) a Σ5 symmetric tilt GB and (c, d) a Σ5 twist GB in LLZO. Reproduced with permission from ref (82). Copyright 2018, American Chemical Society.
Figure 7
Figure 7. (a) Calculated bandgaps of various solid electrolytes in the bulk and in the vicinity of GBs. Isosurface plots of (b) a hole polaron in Li3OCl and (c) an electron polaron in Li3InCl6. (d) Adiabatic potential energy surface associated with the hopping of each polaron. Reproduced with permission under a CC BY 4.0 license from ref (18). Copyright 2023, Wiley-VCH.
References
This article references 83 other publications.
- 1Grey, C. P.; Hall, D. S. Prospects for Lithium-Ion Batteries and beyond─a 2030 Vision. Nat. Commun. 2020, 11 (1), 6279, DOI: 10.1038/s41467-020-19991-41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXisFemu7%252FK&md5=fa9d0069ae9b095d300a78f0cc7c444cProspects for lithium-ion batteries and beyond-a 2030 visionGrey, Clare P.; Hall, David S.Nature Communications (2020), 11 (1), 6279CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)A review. It would be unwise to assume 'conventional' lithium-ion batteries are approaching the end of their era and so we discuss current strategies to improve the current and next generation systems, where a holistic approach will be needed to unlock higher energy d. while also maintaining lifetime and safety. We end by briefly reviewing areas where fundamental science advances will be needed to enable revolutionary new battery systems.
- 2Tian, Y.; Zeng, G.; Rutt, A.; Shi, T.; Kim, H.; Wang, J.; Koettgen, J.; Sun, Y.; Ouyang, B.; Chen, T.; Lun, Z.; Rong, Z.; Persson, K.; Ceder, G. Promises and Challenges of Next-Generation “Beyond Li-Ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev. 2021, 121 (3), 1623– 1669, DOI: 10.1021/acs.chemrev.0c007672https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXis1Krtr3I&md5=52d967164a85b111c6f9ee02bea85e87Promises and challenges of next-generation "beyond lithium-ion" batteries for electric vehicles and grid decarbonizationTian, Yaosen; Zeng, Guobo; Rutt, Ann; Shi, Tan; Kim, Haegyeom; Wang, Jingyang; Koettgen, Julius; Sun, Yingzhi; Ouyang, Bin; Chen, Tina; Lun, Zhengyan; Rong, Ziqin; Persson, Kristin; Ceder, GerbrandChemical Reviews (Washington, DC, United States) (2021), 121 (3), 1623-1669CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. The tremendous improvement in performance and cost of lithium-ion batteries (LIBs) have made them the technol. of choice for elec. energy storage. While established battery chemistries and cell architectures for Li-ion batteries achieve good power and energy d., LIBs are unlikely to meet all the performance, cost, and scaling targets required for energy storage, in particular, in large-scale applications such as electrified transportation and grids. The demand to further reduce cost and/or increase energy d., as well as the growing concern related to natural resource needs for Li-ion have accelerated the investigation of so-called "beyond Li-ion" technologies. In this review, we will discuss the recent achievements, challenges, and opportunities of four important "beyond Li-ion" technologies: Na-ion batteries, K-ion batteries, all-solid-state batteries, and multivalent batteries. The fundamental science behind the challenges, and potential solns. toward the goals of a low-cost and/or high-energy-d. future, are discussed in detail for each technol. While it is unlikely that any given new technol. will fully replace Li-ion in the near future, "beyond Li-ion" technologies should be thought of as opportunities for energy storage to grow into mid/large-scale applications.
- 3Thackeray, M. M.; Wolverton, C.; Isaacs, E. D. Electrical Energy Storage for Transportation─Approaching the Limits of, and Going beyond, Lithium-Ion Batteries. Energy Environ. Sci. 2012, 5 (7), 7854– 7863, DOI: 10.1039/c2ee21892e3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XptVWku70%253D&md5=d681fdb77cf76bcc104bd3726dabddb8Electrical energy storage for transportation-approaching the limits of, and going beyond, lithium-ion batteriesThackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D.Energy & Environmental Science (2012), 5 (7), 7854-7863CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. The escalating and unpredictable cost of oil, the concn. of major oil resources in the hands of a few politically sensitive nations, and the long-term impact of CO2 emissions on global climate constitute a major challenge for the 21st century. They also constitute a major incentive to harness alternative sources of energy and means of vehicle propulsion. Today's lithium-ion batteries, although suitable for small-scale devices, do not yet have sufficient energy or life for use in vehicles that would match the performance of internal combustion vehicles. Energy densities 2 and 5 times greater are required to meet the performance goals of a future generation of plug-in hybrid-elec. vehicles (PHEVs) with a 40-80 mi all-elec. range, and all-elec. vehicles (EVs) with a 300-400 mi range, resp. Major advances have been made in lithium-battery technol. over the past two decades by the discovery of new materials and designs through intuitive approaches, exptl. and predictive reasoning, and meticulous control of surface structures and chem. reactions. Further improvements in energy d. of factors of two to three may yet be achievable for current day lithium-ion systems; factors of five or more may be possible for lithium-oxygen systems, ultimately leading to our ability to confine extremely high potential energy in a small vol. without compromising safety, but only if daunting technol. barriers can be overcome.
- 4Choi, J. W.; Aurbach, D. Promise and Reality of Post-Lithium-Ion Batteries with High Energy Densities. Nat. Rev. Mater. 2016, 1 (4), 16013, DOI: 10.1038/natrevmats.2016.134https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVert7k%253D&md5=3d2782c5ebf801e43442f01f2206379fPromise and reality of post-lithium-ion batteries with high energy densitiesChoi, Jang Wook; Aurbach, DoronNature Reviews Materials (2016), 1 (4), 16013CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Energy d. is the main property of rechargeable batteries that has driven the entire technol. forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead-acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-elec. vehicles. In this Review, we present a crit. overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technol., and also evaluate these materials under com. cell configurations.
- 5Frith, J. T.; Lacey, M. J.; Ulissi, U. A Non-Academic Perspective on the Future of Lithium-Based Batteries. Nat. Commun. 2023, 14 (1), 420, DOI: 10.1038/s41467-023-35933-25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhvFCis78%253D&md5=fa41aef9f4ff4b655e62d488c4b10fc8A non-academic perspective on the future of lithium-based batteriesFrith, James T.; Lacey, Matthew J.; Ulissi, UldericoNature Communications (2023), 14 (1), 420CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Abstr.: In the field of lithium-based batteries, there is often a substantial divide between academic research and industrial market needs. This is in part driven by a lack of peer-reviewed publications from industry. Here we present a non-academic view on applied research in lithium-based batteries to sharpen the focus and help bridge the gap between academic and industrial research. We focus our discussion on key metrics and challenges to be considered when developing new technologies in this industry. We also explore the need to consider various performance aspects in unison when developing a new material/technol. Moreover, we also investigate the suitability of supply chains, sustainability of materials and the impact on system-level cost as factors that need to be accounted for when working on new technologies. With these considerations in mind, we then assess the latest developments in the lithium-based battery industry, providing our views on the challenges and prospects of various technologies.
- 6Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 1278– 1291, DOI: 10.1038/s41563-019-0431-36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7I&md5=582754f689db47f9562c6f4201f150bfFundamentals of inorganic solid-state electrolytes for batteriesFamprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.; Islam, M. Saiful; Masquelier, ChristianNature Materials (2019), 18 (12), 1278-1291CODEN: NMAACR; ISSN:1476-1122. (Nature Research)A review. In the crit. area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-d. and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorg. solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochem. and mech. properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of phys. contact, the solns. to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials.
- 7Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2, 16103, DOI: 10.1038/natrevmats.2016.1037https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXislGitr0%253D&md5=be4704bc600127083842361f9e75c578Lithium battery chemistries enabled by solid-state electrolytesManthiram, Arumugam; Yu, Xingwen; Wang, ShaofeiNature Reviews Materials (2017), 2 (3), 16103CODEN: NRMADL; ISSN:2058-8437. (Nature Publishing Group)Solid-state electrolytes are attracting increasing interest for electrochem. energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liq. or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aq. electrochem. energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic cond., electrochem. stability and mech. properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
- 8Xiao, Y.; Wang, Y.; Bo, S.-H.; Kim, J. C.; Miara, L. J.; Ceder, G. Understanding Interface Stability in Solid-State Batteries. Nat. Rev. Mater. 2020, 5 (2), 105– 126, DOI: 10.1038/s41578-019-0157-58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVert7jP&md5=7cfe14defb708589a92617809ef0b029Understanding interface stability in solid-state batteriesXiao, Yihan; Wang, Yan; Bo, Shou-Hang; Kim, Jae Chul; Miara, Lincoln J.; Ceder, GerbrandNature Reviews Materials (2020), 5 (2), 105-126CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Solid-state batteries (SSBs) using a solid electrolyte show potential for providing improved safety as well as higher energy and power d. compared with conventional Li-ion batteries. However, two crit. bottlenecks remain: the development of solid electrolytes with ionic conductivities comparable to or higher than those of conventional liq. electrolytes and the creation of stable interfaces between SSB components, including the active material, solid electrolyte and conductive additives. Although the first goal has been achieved in several solid ionic conductors, the high impedance at various solid/solid interfaces remains a challenge. Recently, computational models based on ab initio calcns. have successfully predicted the stability of solid electrolytes in various systems. In addn., a large amt. of exptl. data has been accumulated for different interfaces in SSBs. In this Review, we summarize the exptl. findings for various classes of solid electrolytes and relate them to computational predictions, with the aim of providing a deeper understanding of the interfacial reactions and insight for the future design and engineering of interfaces in SSBs. We find that, in general, the electrochem. stability and interfacial reaction products can be captured with a small set of chem. and phys. principles.
- 9Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H.-H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P.; Giordano, L.; Shao-Horn, Y. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. Chem. Rev. 2016, 116 (1), 140– 162, DOI: 10.1021/acs.chemrev.5b005639https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XjtF2itA%253D%253D&md5=50c8d626d5489138b35dd462054cfa98Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion ConductionBachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis; Chang, Hao-Hsun; Pour, Nir; Lux, Simon F.; Paschos, Odysseas; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Giordano, Livia; Shao-Horn, YangChemical Reviews (Washington, DC, United States) (2016), 116 (1), 140-162CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochem. energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the cond. through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielec. consts. and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Exptl. studies and theor. results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the phys. parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors.
- 10Janek, J.; Zeier, W. G. Challenges in Speeding up Solid-State Battery Development. Nat. Energy 2023, 8 (3), 230– 240, DOI: 10.1038/s41560-023-01208-9There is no corresponding record for this reference.
- 11Guo, Y.; Wu, S.; He, Y.-B.; Kang, F.; Chen, L.; Li, H.; Yang, Q.-H. Solid-State Lithium Batteries: Safety and Prospects. eScience 2022, 2 (2), 138– 163, DOI: 10.1016/j.esci.2022.02.008There is no corresponding record for this reference.
- 12Bates, A. M.; Preger, Y.; Torres-Castro, L.; Harrison, K. L.; Harris, S. J.; Hewson, J. Are Solid-State Batteries Safer than Lithium-Ion Batteries?. Joule 2022, 6 (4), 742– 755, DOI: 10.1016/j.joule.2022.02.00712https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhtFaqt7bJ&md5=24a4834ae6108de0381068e13ef6925cAre solid-state batteries safer than lithium-ion batteries?Bates, Alex M.; Preger, Yuliya; Torres-Castro, Loraine; Harrison, Katharine L.; Harris, Stephen J.; Hewson, JohnJoule (2022), 6 (4), 742-755CODEN: JOULBR; ISSN:2542-4351. (Cell Press)A review. All-solid-state batteries are often assumed to be safer than conventional Li-ion ones. In this work, we present the first thermodn. models to quant. evaluate solid-state and Li-ion battery heat release under several failure scenarios. The solid-state battery anal. is carried out with an Li7La3Zr2O12 solid electrolyte but can be extended to other configurations using the accompanying spreadsheet. We consider solid-state batteries that include a relatively small amt. of liq. electrolyte, which is often added at the cathode to reduce interfacial resistance. While the addn. of small amts. of liq. electrolyte increases heat release under specific failure scenarios, it may be small enough that other considerations, such as manufacturability and performance, are more important com. We show that short-circuited all-solid-state batteries can reach temps. significantly higher than conventional Li-ion, which could lead to fire through flammable packaging and/or nearby materials. Our work highlights the need for quant. safety analyses of solid-state batteries.
- 13Zhao, Q.; Stalin, S.; Zhao, C.-Z.; Archer, L. A. Designing Solid-State Electrolytes for Safe, Energy-Dense Batteries. Nat. Rev. Mater. 2020, 5 (3), 229– 252, DOI: 10.1038/s41578-019-0165-513https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtFyks74%253D&md5=d5aa2c58ad523b3289f44f0a2499892fDesigning solid-state electrolytes for safe, energy-dense batteriesZhao, Qing; Stalin, Sanjuna; Zhao, Chen-Zi; Archer, Lynden A.Nature Reviews Materials (2020), 5 (3), 229-252CODEN: NRMADL; ISSN:2058-8437. (Nature Research)A review. Abstr.: Solid-state electrolytes (SSEs) have emerged as high-priority materials for safe, energy-dense and reversible storage of electrochem. energy in batteries. In this Review, we assess recent progress in the design, synthesis and anal. of SSEs, and identify key failure modes, performance limitations and design concepts for creating SSEs to meet requirements for practical applications. We provide an overview of the development and characteristics of SSEs, followed by anal. of ion transport in the bulk and at interfaces based on different single-valent (Li+, Na+, K+) and multivalent (Mg2+, Zn2+, Ca2+, Al3+) cation carriers of contemporary interest. We analyze the progress in overcoming issues assocd. with the poor ionic cond. and high interfacial resistance of inorg. SSEs and the poor oxidative stability and cation transference nos. of polymer SSEs. Perspectives are provided on the design requirements for future generations of SSEs, with a focus on the chem., geometric, mech., electrochem. and interfacial transport features required to accelerate progress towards practical solid-state batteries in which metals are paired with energetic cathode chemistries, including Ni-rich and Li-rich intercalating materials, sustainable org. materials, S8, O2 and CO2.
- 14Albertus, P.; Anandan, V.; Ban, C.; Balsara, N.; Belharouak, I.; Buettner-Garrett, J.; Chen, Z.; Daniel, C.; Doeff, M.; Dudney, N. J.; Dunn, B.; Harris, S. J.; Herle, S.; Herbert, E.; Kalnaus, S.; Libera, J. A.; Lu, D.; Martin, S.; McCloskey, B. D.; McDowell, M. T.; Meng, Y. S.; Nanda, J.; Sakamoto, J.; Self, E. C.; Tepavcevic, S.; Wachsman, E.; Wang, C.; Westover, A. S.; Xiao, J.; Yersak, T. Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries. ACS Energy Lett. 2021, 1399– 1404, DOI: 10.1021/acsenergylett.1c0044514https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmvVCmsLY%253D&md5=8de2940c82b1d2767d98def586dae92eChallenges for and Pathways toward Li-Metal-Based All-Solid-State BatteriesAlbertus, Paul; Anandan, Venkataramani; Ban, Chunmei; Balsara, Nitash; Belharouak, Ilias; Buettner-Garrett, Josh; Chen, Zonghai; Daniel, Claus; Doeff, Marca; Dudney, Nancy J.; Dunn, Bruce; Harris, Stephen J.; Herle, Subramanya; Herbert, Eric; Kalnaus, Sergiy; Libera, Joesph A.; Lu, Dongping; Martin, Steve; McCloskey, Bryan D.; McDowell, Matthew T.; Meng, Y. Shirley; Nanda, Jagjit; Sakamoto, Jeff; Self, Ethan C.; Tepavcevic, Sanja; Wachsman, Eric; Wang, Chunsheng; Westover, Andrew S.; Xiao, Jie; Yersak, ThomasACS Energy Letters (2021), 6 (4), 1399-1404CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Solid-state batteries hold great promise for high-energy batteries for elec. vehicles and other applications. While the potential is great, success is contingent on solving crit. challenges in materials science, processing science, and fabrication of practical full cells. This focus article has outlined several key challenges in the hope that they will encourage and inspire solns. and the eventual realization of high-energy solid-state batteries.
- 15Xia, S.; Wu, X.; Zhang, Z.; Cui, Y.; Liu, W. Practical Challenges and Future Perspectives of All-Solid-State Lithium-Metal Batteries. Chem. 2019, 5 (4), 753– 785, DOI: 10.1016/j.chempr.2018.11.01315https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXnsVejsbs%253D&md5=8a74f693b991ab0ee331cd47a06ddeaePractical Challenges and Future Perspectives of All-Solid-State Lithium-Metal BatteriesXia, Shuixin; Wu, Xinsheng; Zhang, Zhichu; Cui, Yi; Liu, WeiChem (2019), 5 (4), 753-785CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)The fundamental understandings and technol. innovations in lithium-ion batteries are essential for delivering high energy d., stable cyclability, and cost-effective energy storages with the growing demands in the applications of elec. vehicles and smart grid. Solid-state electrolytes (SSEs) are more promising than org. liq. electrolyte in terms of excellent safety in developing lithium-metal anode as well as other high-capacity cathode chemistries, such as sulfur and oxygen. Considerable efforts have been made to give birth to the superionic conductors with ionic conductivities higher than 10-3 S cm-1 at room temp. However, the high interfacial impedances from the poor compatibility of SSEs with electrodes limit their practical applications, which are discussed in this review. Furthermore, the recent advances and crit. challenges for all-solid-state lithium-metal batteries based on the cathode materials of lithium-intercalation compds., sulfur, and oxygen are overviewed, and their future developments are also prospected.
- 16Ning, Z.; Li, G.; Melvin, D. L. R.; Chen, Y.; Bu, J.; Spencer-Jolly, D.; Liu, J.; Hu, B.; Gao, X.; Perera, J.; Gong, C.; Pu, S. D.; Zhang, S.; Liu, B.; Hartley, G. O.; Bodey, A. J.; Todd, R. I.; Grant, P. S.; Armstrong, D. E. J.; Marrow, T. J.; Monroe, C. W.; Bruce, P. G. Dendrite Initiation and Propagation in Lithium Metal Solid-State Batteries. Nature 2023, 618 (7964), 287– 293, DOI: 10.1038/s41586-023-05970-416https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhtFOksrjJ&md5=77e737ef2df085a5ee9e5117ece77427Dendrite initiation and propagation in lithium metal solid-state batteriesNing, Ziyang; Li, Guanchen; Melvin, Dominic L. R.; Chen, Yang; Bu, Junfu; Spencer-Jolly, Dominic; Liu, Junliang; Hu, Bingkun; Gao, Xiangwen; Perera, Johann; Gong, Chen; Pu, Shengda D.; Zhang, Shengming; Liu, Boyang; Hartley, Gareth O.; Bodey, Andrew J.; Todd, Richard I.; Grant, Patrick S.; Armstrong, David E. J.; Marrow, T. James; Monroe, Charles W.; Bruce, Peter G.Nature (London, United Kingdom) (2023), 618 (7964), 287-293CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are sep. processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is detd. by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population d. and c.d., propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, c.d., stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the no. of cycles before short circuit in cells in which dendrites have initiated.
- 17Dawson, J. A.; Canepa, P.; Famprikis, T.; Masquelier, C.; Islam, M. S. Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries. J. Am. Chem. Soc. 2018, 140 (1), 362– 368, DOI: 10.1021/jacs.7b1059317https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhvFCktLvP&md5=af5abf35aa307fc19351588fc3702227Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State BatteriesDawson, James A.; Canepa, Pieremanuele; Famprikis, Theodosios; Masquelier, Christian; Islam, M. SaifulJournal of the American Chemical Society (2018), 140 (1), 362-368CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Solid electrolytes are generating considerable interest for all-solid-state Li-ion batteries to address safety and performance issues. Grain boundaries have a significant influence on solid electrolytes and are key hurdles that must be overcome for their successful application. However, grain boundary effects on ionic transport are not fully understood, esp. at the at. scale. The Li-rich anti-perovskite Li3OCl is a promising solid electrolyte, although there is debate concerning the precise Li-ion migration barriers and cond. Using Li3OCl as a model polycryst. electrolyte, we apply large-scale mol. dynamics simulations to analyze the ionic transport at stable grain boundaries. Our results predict high concns. of grain boundaries and clearly show that Li-ion cond. is severely hindered through the grain boundaries. The activation energies for Li-ion conduction traversing the grain boundaries are consistently higher than that of the bulk crystal, confirming the high grain boundary resistance in this material. Using our results, we propose a polycryst. model to quantify the impact of grain boundaries on cond. as a function of grain size. Such insights provide valuable fundamental understanding of the role of grain boundaries and how tailoring the microstructure can lead to the optimization of new high-performance solid electrolytes.
- 18Quirk, J. A.; Dawson, J. A. Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors. Adv. Energy Mater. 2023, 13, 2301114, DOI: 10.1002/aenm.20230111418https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsFaht7rP&md5=5e9a278988cba0b447fc51bbc5bf1817Design Principles for Grain Boundaries in Solid-State Lithium-Ion ConductorsQuirk, James A.; Dawson, James A.Advanced Energy Materials (2023), 13 (32), 2301114CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Lithium dendrite formation and insufficient ionic cond. remain primary concerns for the utilization of solid-state batteries. Given that the interpretation of exptl. results for polycryst. solid electrolytes can be difficult, computational techniques are invaluable for providing insight at the at. scale. Here, first-principles calcns. are carried out on representative grain boundaries in four important solid electrolytes, namely, an anti-perovskite oxide, Li3OCl, and its hydrated counterpart, Li2OHCl, a thiophosphate, Li3PS4, and a halide, Li3InCl6, to develop the first generally applicable design principles for grain boundaries in solid electrolytes for solid-state batteries. The significantly different impacts that grain boundaries have on electronic structure and transport, ion cond. and correlated ion dynamics are demonstrated. The results show that even when grain boundaries do not significantly impact ionic cond., they can still strongly perturb the electronic structure and contribute to potential lithium dendrite propagation. It is also illustrated, for the first time, how correlated motion, including the so-called paddle-wheel mechanism, can vary substantially at grain boundaries. These findings reveal the dramatically different behavior of solid electrolytes at the microscale compared to the bulk and its potential consequences and benefits for the design of solid-state batteries. These design principles are expected to aid the synthesis and engineering of solid electrolytes at the microscale for preventing dendrite propagation and accelerating ion transport.
- 19Milan, E.; Pasta, M. The Role of Grain Boundaries in Solid-State Li-Metal Batteries. Materials Futures 2023, 2 (1), 013501, DOI: 10.1088/2752-5724/aca703There is no corresponding record for this reference.
- 20Zhang, Z.; Shao, Y.; Lotsch, B.; Hu, Y.-S.; Li, H.; Janek, J.; Nazar, L. F.; Nan, C.-W.; Maier, J.; Armand, M.; Chen, L. New Horizons for Inorganic Solid State Ion Conductors. Energy Environ. Sci. 2018, 11 (8), 1945– 1976, DOI: 10.1039/C8EE01053F20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFCmsLjJ&md5=446ed0fac045cbb01d3747b81e7577e9New horizons for inorganic solid state ion conductorsZhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina; Hu, Yong-Sheng; Li, Hong; Janek, Jurgen; Nazar, Linda F.; Nan, Ce-Wen; Maier, Joachim; Armand, Michel; Chen, LiquanEnergy & Environmental Science (2018), 11 (8), 1945-1976CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. Among the contenders in the new generation energy storage arena, all-solid-state batteries (ASSBs) have emerged as particularly promising, owing to their potential to exhibit high safety, high energy d. and long cycle life. The relatively low cond. of most solid electrolytes and the often sluggish charge transfer kinetics at the interface between solid electrolyte and electrode layers are considered to be amongst the major challenges facing ASSBs. This review presents an overview of the state of the art in solid lithium and sodium ion conductors, with an emphasis on inorg. materials. The correlations between the compn., structure and cond. of these solid electrolytes are illustrated and strategies to boost ion cond. are proposed. In particular, the high grain boundary resistance of solid oxide electrolytes is identified as a challenge. Crit. issues of solid electrolytes beyond ion cond. are also discussed with respect to their potential problems for practical applications. The chem. and electrochem. stabilities of solid electrolytes are discussed, as are chemo-mech. effects which have been overlooked to some extent. Furthermore, strategies to improve the practical performance of ASSBs, including optimizing the interface between solid electrolytes and electrode materials to improve stability and lower charge transfer resistance are also suggested.
- 21Priester, L. Grain Boundaries: From Theory to Engineering; Springer: New York, 2013.There is no corresponding record for this reference.
- 22Dawson, J. A.; Canepa, P.; Clarke, M. J.; Famprikis, T.; Ghosh, D.; Islam, M. S. Toward Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid Electrolytes. Chem. Mater. 2019, 31 (14), 5296– 5304, DOI: 10.1021/acs.chemmater.9b0179422https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXht1CqsbvJ&md5=50b49e9fb95a443c5f40ee8e9af23d9dToward Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid ElectrolytesDawson, James A.; Canepa, Pieremanuele; Clarke, Matthew J.; Famprikis, Theodosios; Ghosh, Dibyajyoti; Islam, M. SaifulChemistry of Materials (2019), 31 (14), 5296-5304CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liq. electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic cond. is the apparently reduced grain boundary resistance of sulfide solid electrolytes compared to their oxide counterparts, but this is not fully established. Using 2 model electrolyte systems, Na3PS4 and Na3PO4, the authors apply a novel microscale simulation approach to analyze ionic transport in polycryst. materials with various grain vols. For Na3PO4, high grain boundary resistance is found, with the Na-ion cond. decreasing with decreasing grain vol. For Na3PS4, the overall influence of grain boundaries (GBs) is significantly reduced compared to the oxide. Detailed anal. reveals a minimal change in the local structures and Na-ion conduction mechanism between bulk and polycryst. Na3PS4, whereas the change is far more substantial for Na3PO4, with evidence of over-coordination of Na ions at the GBs. The microscale approach helps to explain the fundamentally different influences of GBs on ion transport in phosphate and thiophosphate solid electrolytes.
- 23Han, F.; Westover, A. S.; Yue, J.; Fan, X.; Wang, F.; Chi, M.; Leonard, D. N.; Dudney, N. J.; Wang, H.; Wang, C. High Electronic Conductivity as the Origin of Lithium Dendrite Formation within Solid Electrolytes. Nat. Energy 2019, 4 (3), 187– 196, DOI: 10.1038/s41560-018-0312-z23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmslGktbc%253D&md5=bc9f7d5bd77f27144060254fea0474f1High electronic conductivity as the origin of lithium dendrite formation within solid electrolytesHan, Fudong; Westover, Andrew S.; Yue, Jie; Fan, Xiulin; Wang, Fei; Chi, Miaofang; Leonard, Donovan N.; Dudney, Nancy J.; Wang, Howard; Wang, ChunshengNature Energy (2019), 4 (3), 187-196CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Solid electrolytes (SEs) are widely considered as an 'enabler' of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li7La3Zr2O12 (LLZO) and Li2S-P2S5 is actually much easier than that in liq. electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concn. profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li3PS4) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concn. in LiPON can be obsd., we visualize the direct deposition of Li inside the bulk LLZO and Li3PS4. Our findings suggest the high electronic cond. of LLZO and Li3PS4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic cond., rather than further increasing the ionic cond. of SEs, is therefore crit. for the success of all-solid-state Li batteries.
- 24Liu, X.; Garcia-Mendez, R.; Lupini, A. R.; Cheng, Y.; Hood, Z. D.; Han, F.; Sharafi, A.; Idrobo, J. C.; Dudney, N. J.; Wang, C.; Ma, C.; Sakamoto, J.; Chi, M. Local Electronic Structure Variation Resulting in Li ‘Filament’ Formation within Solid Electrolytes. Nat. Mater. 2021, 20 (11), 1485– 1490, DOI: 10.1038/s41563-021-01019-x24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXht1WqtrjF&md5=8e49128d7024b4efac3bf42cb0bd7c51Local electronic structure variation resulting in lithium filament formation within solid electrolytesLiu, Xiaoming; Garcia-Mendez, Regina; Lupini, Andrew R.; Cheng, Yongqiang; Hood, Zachary D.; Han, Fudong; Sharafi, Asma; Idrobo, Juan Carlos; Dudney, Nancy J.; Wang, Chunsheng; Ma, Cheng; Sakamoto, Jeff; Chi, MiaofangNature Materials (2021), 20 (11), 1485-1490CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Solid electrolytes hold great promise for enabling the use of Li metal anodes. The main problem is that during cycling, Li can infiltrate along grain boundaries and cause short circuits, resulting in potentially catastrophic battery failure. At present, this phenomenon is not well understood. Here, through electron microscopy measurements on a representative system, Li7La3Zr2O12, we discover that Li infiltration in solid oxide electrolytes is strongly assocd. with local electronic band structure. About half of the Li7La3Zr2O12 grain boundaries were found to have a reduced bandgap, around 1-3 eV, making them potential channels for leakage current. Instead of combining with electrons at the cathode, Li+ ions are hence prematurely reduced by electrons at grain boundaries, forming local Li filaments. The eventual interconnection of these filaments results in a short circuit. Our discovery reveals that the grain-boundary electronic cond. must be a primary concern for optimization in future solid-state battery design.
- 25Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors. Nat. Mater. 2015, 14 (10), 1026– 1031, DOI: 10.1038/nmat436925https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlCksb%252FI&md5=114ad3946493cf35ef3ee5d65e37c2d7Design principles for solid-state lithium superionic conductorsWang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, GerbrandNature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
- 26He, X.; Zhu, Y.; Mo, Y. Origin of Fast Ion Diffusion in Super-Ionic Conductors. Nat. Commun. 2017, 8 (May), 15893, DOI: 10.1038/ncomms1589326https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVeqtbjM&md5=ca442e7d39979b975b99586daaabf1f9Origin of fast ion diffusion in super-ionic conductorsHe, Xingfeng; Zhu, Yizhou; Mo, YifeiNature Communications (2017), 8 (), 15893CODEN: NCAOBW; ISSN:2041-1723. (Nature Publishing Group)Super-ionic conductor materials have great potential to enable novel technologies in energy storage and conversion. However, it is not yet understood why only a few materials can deliver exceptionally higher ionic cond. than typical solids or how one can design fast ion conductors following simple principles. Using ab initio modeling, here we show that fast diffusion in super-ionic conductors does not occur through isolated ion hopping as is typical in solids, but instead proceeds through concerted migrations of multiple ions with low energy barriers. Furthermore, we elucidate that the low energy barriers of the concerted ionic diffusion are a result of unique mobile ion configurations and strong mobile ion interactions in super-ionic conductors. Our results provide a general framework and universal strategy to design solid materials with fast ionic diffusion.
- 27Poletayev, A. D.; Dawson, J. A.; Islam, M. S.; Lindenberg, A. M. Defect-Driven Anomalous Transport in Fast-Ion Conducting Solid Electrolytes. Nat. Mater. 2022, 21 (9), 1066– 1073, DOI: 10.1038/s41563-022-01316-z27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFOgsLzK&md5=6afcc953f75686af1d61700bcee60022Defect-driven anomalous transport in fast-ion conducting solid electrolytesPoletayev, Andrey D.; Dawson, James A.; Islam, M. Saiful; Lindenberg, Aaron M.Nature Materials (2022), 21 (9), 1066-1073CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)Solid-state ionic conduction is a key enabler of electrochem. energy storage and conversion. The mechanistic connections between material processing, defect chem., transport dynamics and practical performance are of considerable importance but remain incomplete. Here, inspired by studies of fluids and biophys. systems, we re-examine anomalous diffusion in the iconic two-dimensional fast-ion conductors, the β- and β''-aluminas. Using large-scale simulations, we reproduce the frequency dependence of alternating-current ionic cond. data. We show how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder and leads to persistent subdiffusive ion transport at macroscopic timescales. We deconvolute the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects, and geometric crowding on ionic cond. Finally, our characterization of memory effects in transport connects atomistic defect chem. to macroscopic performance with minimal assumptions and enables mechanism-driven 'atoms-to-device' optimization of fast-ion conductors.
- 28Ong, S. P.; Mo, Y.; Richards, W. D.; Miara, L.; Lee, H. S.; Ceder, G. Phase Stability, Electrochemical Stability and Ionic Conductivity of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) Family of Superionic Conductors. Energy Environ. Sci. 2013, 6 (1), 148– 156, DOI: 10.1039/C2EE23355J28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhvVKqtLfM&md5=eeb3311cb7157b8e8471315d471251e9Phase stability, electrochemical stability and ionic conductivity of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductorsOng, Shyue Ping; Mo, Yifei; Richards, William Davidson; Miara, Lincoln; Lee, Hyo Sug; Ceder, GerbrandEnergy & Environmental Science (2013), 6 (1), 148-156CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)We present an investigation of the phase stability, electrochem. stability and Li+ cond. of the Li10±1MP2X12 (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors using first principles calcns. The Li10GeP2S12 (LGPS) superionic conductor has the highest Li+ cond. reported to date, with excellent electrochem. performance demonstrated in a Li-ion rechargeable battery. Our results show that isovalent cation substitutions of Ge4+ have a small effect on the relevant intrinsic properties, with Li10SiP2S12 and Li10SnP2S12 having similar phase stability, electrochem. stability and Li+ cond. as LGPS. Aliovalent cation substitutions (M = Al or P) with compensating changes in the Li+ concn. also have a small effect on the Li+ cond. in this structure. Anion substitutions, however, have a much larger effect on these properties. The oxygen-substituted Li10MP2O12 compds. are predicted not to be stable (with equil. decompn. energies >90 meV per atom) and have much lower Li+ conductivities than their sulfide counterparts. The selenium-substituted Li10MP2Se12 compds., on the other hand, show a marginal improvement in cond., but at the expense of reduced electrochem. stability. We also studied the effect of lattice parameter changes on the Li+ cond. and found the same asymmetry in behavior between increases and decreases in the lattice parameters, i.e., decreases in the lattice parameters lower the Li+ cond. significantly, while increases in the lattice parameters increase the Li+ cond. only marginally. Based on these results, we conclude that the size of the S2- is near optimal for Li+ conduction in this structural framework.
- 29Richards, W. D.; Miara, L. J.; Wang, Y.; Kim, J. C.; Ceder, G. Interface Stability in Solid-State Batteries. Chem. Mater. 2016, 28 (1), 266– 273, DOI: 10.1021/acs.chemmater.5b0408229https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvFKltbrP&md5=5cfe0951cc716630f75508770bc9e1e3Interface Stability in Solid-State BatteriesRichards, William D.; Miara, Lincoln J.; Wang, Yan; Kim, Jae Chul; Ceder, GerbrandChemistry of Materials (2016), 28 (1), 266-273CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Development of high cond. solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because exptl. evaluation of the interface can be very difficult. In this work, we develop a computational methodol. to examine the thermodn. of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with exptl. interfacial observations and battery performance. We calc. that thiophosphate electrolytes have esp. high reactivity with high voltage cathodes and a narrow electrochem. stability window. We also find that a no. of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. As a ref. for experimentalists, we tabulate the stability and expected decompn. products for a wide range of electrolyte, coating, and electrode materials including a no. of high-performing combinations that have not yet been attempted exptl.
- 30Schwietert, T. K.; Arszelewska, V. A.; Wang, C.; Yu, C.; Vasileiadis, A.; de Klerk, N. J. J.; Hageman, J.; Hupfer, T.; Kerkamm, I.; Xu, Y.; van der Maas, E.; Kelder, E. M.; Ganapathy, S.; Wagemaker, M. Clarifying the Relationship between Redox Activity and Electrochemical Stability in Solid Electrolytes. Nat. Mater. 2020, 19 (4), 428– 435, DOI: 10.1038/s41563-019-0576-030https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXpsFOruw%253D%253D&md5=75eb3965f4d23b778ec1335aad245702Clarifying the relationship between redox activity and electrochemical stability in solid electrolytesSchwietert, Tammo K.; Arszelewska, Violetta A.; Wang, Chao; Yu, Chuang; Vasileiadis, Alexandros; de Klerk, Niek J. J.; Hageman, Jart; Hupfer, Thomas; Kerkamm, Ingo; Xu, Yaolin; van der Maas, Eveline; Kelder, Erik M.; Ganapathy, Swapna; Wagemaker, MarnixNature Materials (2020), 19 (4), 428-435CODEN: NMAACR; ISSN:1476-1122. (Nature Research)All-solid-state Li-ion batteries promise safer electrochem. energy storage with larger volumetric and gravimetric energy densities. A major concern is the limited electrochem. stability of solid electrolytes and related detrimental electrochem. reactions, esp. because of our restricted understanding. Here we demonstrate for the argyrodite-, garnet- and NASICON-type solid electrolytes that the favorable decompn. pathway is indirect rather than direct, via (de)lithiated states of the solid electrolyte, into the thermodynamically stable decompn. products. The consequence is that the electrochem. stability window of the solid electrolyte is notably larger than predicted for direct decompn., rationalizing the obsd. stability window. The obsd. argyrodite metastable (de)lithiated solid electrolyte phases contribute to the (ir)reversible cycling capacity of all-solid-state batteries, in addn. to the contribution of the decompn. products, comprehensively explaining solid electrolyte redox activity. The fundamental nature of the proposed mechanism suggests this is a key aspect for solid electrolytes in general, guiding interface and material design for all-solid-state batteries.
- 31Haruyama, J.; Sodeyama, K.; Han, L.; Takada, K.; Tateyama, Y. Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion Battery. Chem. Mater. 2014, 26 (14), 4248– 4255, DOI: 10.1021/cm501695931https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVymtLjO&md5=7f33a221907521fc8fce4b4353dcb170Space-Charge Layer Effect at Interface between Oxide Cathode and Sulfide Electrolyte in All-Solid-State Lithium-Ion BatteryHaruyama, Jun; Sodeyama, Keitaro; Han, Liyuan; Takada, Kazunori; Tateyama, YoshitakaChemistry of Materials (2014), 26 (14), 4248-4255CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The authors theor. elucidated the characteristics of the space-charge layer (SCL) at interfaces between oxide cathode and sulfide electrolyte in all-solid-state Li-ion batteries (ASS-LIBs) and the effect of the buffer layer interposition, for the 1st time, via the calcns. with d. functional theory (DFT) + U framework. As a most representative system, the authors examd. the interfaces between LiCoO2 cathode and β-Li3PS4 solid electrolyte (LCO/LPS), and the LiCoO2/LiNbO3/β-Li3PS4 (LCO/LNO/LPS) interfaces with the LiNbO3 buffer layers. The DFT+U calcns., coupling with a systematic procedure for interface matching, showed the stable structures and the electronic states of the interfaces. The LCO/LPS interface has attractive Li adsorption sites and rather disordered structure, whereas the interposition of the LNO buffer layers forms smooth interfaces without Li adsorption sites for both LCO and LPS sides. The calcd. energies of the Li-vacancy formation and the Li migration reveal that subsurface Li in the LPS side can begin to transfer at the under-voltage condition in the LCO/LPS interface, which suggests the SCL growth at the beginning of charging, leading to the interfacial resistance. The LNO interposition suppresses this growth of SCL and provides smooth Li transport paths free from the possible bottlenecks. These aspects on the at. scale will give a useful perspective for the further improvement of the ASS-LIB performance.
- 32Gorai, P.; Famprikis, T.; Singh, B.; Stevanović, V.; Canepa, P. Devil Is in the Defects: Electronic Conductivity in Solid Electrolytes. Chem. Mater. 2021, 33 (18), 7484– 7498, DOI: 10.1021/acs.chemmater.1c0234532https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvFensrnF&md5=3039fb463fef992e2b99b17a6015ed28Defects and electronic conductivity in solid electrolytesGorai, Prashun; Famprikis, Theodosios; Singh, Baltej; Stevanovic, Vladan; Canepa, PieremanueleChemistry of Materials (2021), 33 (18), 7484-7498CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Rechargeable solid-state batteries (SSBs) continue to gain prominence due to their increased safety. However, a no. of outstanding challenges still prevent their adoption in mainstream technol. This study reveals one of the origins of electronic cond., σe, in solid electrolytes (SEs), which is deemed responsible for SSB degrdn., as well as more drastic short-circuit and failure mechanisms. Using first-principles defect calcns. and physics-based models, we predict σe in three topical SEs: Li6PS5Cl and Li6PS5I argyrodites and Na3PS4 for post-Li batteries. We treat SEs as materials with finite band gaps and apply the defect theory of semiconductors to calc. the native defect concns. and assocd. electronic conductivities. Li6PS5Cl, Li6PS5I, and Na3PS4 were synthesized and characterized with UV-vis spectroscopy, which validates our computational approach confirming the occurrence of defects within the band gap of these SEs. The quant. agreement of the predicted σe in these SEs and those measured exptl. strongly suggests that doping by native defects is a major source of electronic cond. in SEs even without considering purposefully introduced dopants and/or grain boundaries. We find that Li6PS5Cl and Li6PS5I are n-type (electrons are the majority carriers), while Na3PS4 is p-type (holes). We suggest general defect engineering strategies pertaining to synthesis protocols to reduce σe in SEs and thereby curtailing the degrdn. mechanism. The methodol. presented here can be extended to est. σe in solid-electrolyte interphases. Our methodol. also provides a quant. measure of the native defects in SEs at different synthesis conditions, which is paramount to understand the effects of defects on the ionic cond.
- 33Li, Y.; Canepa, P.; Gorai, P. Role of Electronic Passivation in Stabilizing the Lithium-LixPOyNz Solid-Electrolyte Interphase. PRX Energy 2022, 1 (2), 23004, DOI: 10.1103/PRXEnergy.1.023004There is no corresponding record for this reference.
- 34Squires, A. G.; Scanlon, D. O.; Morgan, B. J. Native Defects and Their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12. Chem. Mater. 2020, 32 (5), 1876– 1886, DOI: 10.1021/acs.chemmater.9b0431934https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVGhtbnK&md5=d04a8d8c646be8aa5e6b1ebf122005caNative Defects and Their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12Squires, Alexander G.; Scanlon, David O.; Morgan, Benjamin J.Chemistry of Materials (2020), 32 (5), 1876-1886CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The Li-stuffed garnets LixM2M3'O12 are promising Li-ion solid electrolytes with potential use in solid-state batteries. One strategy for optimizing ionic conductivities in these materials is to tune lithium stoichiometries through aliovalent doping, which is often assumed to produce proportionate nos. of charge-compensating Li vacancies. The native defect chem. of the Li-stuffed garnets, and their response to doping, however, are not well understood, and it is unknown to what degree a simple vacancy-compensation model is valid. Here, we report hybrid d.-functional-theory calcns. of a broad range of native defects in the prototypical Li-garnet Li7La3Zr2O12 . We calc. equil. defect concns. as a function of synthesis conditions, and model the response of these defect populations to extrinsic doping. We predict a rich defect chem. that includes Li and O vacancies and interstitials, and significant nos. of cation-antisite defects. Under reducing conditions, O vacancies act as color-centers by trapping electrons. We find that supervalent (donor) doping does not produce charge compensating Li vacancies under all synthesis conditions; under Li-rich / Zr-poor conditions the dominant compensating defects are LiZr antisites, and Li stoichiometries strongly deviate from those predicted by simple "vacancy compensation" models.
- 35Zhu, F.; Islam, M. S.; Zhou, L.; Gu, Z.; Liu, T.; Wang, X.; Luo, J.; Nan, C.-W.; Mo, Y.; Ma, C. Single-Atom-Layer Traps in a Solid Electrolyte for Lithium Batteries. Nat. Commun. 2020, 11 (1), 1828, DOI: 10.1038/s41467-020-15544-x35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXntFOhsLc%253D&md5=d7fe46a3a3c292b94a78aefdf0b5c936Single-atom-layer traps in a solid electrolyte for lithium batteriesZhu, Feng; Islam, Md. Shafiqul; Zhou, Lin; Gu, Zhenqi; Liu, Ting; Wang, Xinchao; Luo, Jun; Nan, Ce-Wen; Mo, Yifei; Ma, ChengNature Communications (2020), 11 (1), 1828CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)In order to fully understand the lithium-ion transport mechanism in solid electrolytes for batteries, not only the periodic lattice but also the non-periodic features that disrupt the ideal periodicity must be comprehensively studied. At present only a limited no. of non-periodic features such as point defects and grain boundaries are considered in mechanistic studies. Here, we discover an addnl. type of non-periodic feature that significantly influences ionic transport; this feature is termed a "single-atom-layer trap" (SALT). In a prototype solid electrolyte Li0.33La0.56TiO3, the single-atom-layer defects that form closed loops, i.e., SALTs, are found ubiquitous by at.-resoln. electron microscopy. According to ab initio calcns., these defect loops prevent large vols. of materials from participating in ionic transport, and thus severely degrade the total cond. This discovery points out the urgency of thoroughly investigating different types of non-periodic features, and motivates similar studies for other solid electrolytes.
- 36Shin, D. O.; Oh, K.; Kim, K. M.; Park, K.-Y.; Lee, B.; Lee, Y.-G.; Kang, K. Synergistic Multi-Doping Effects on the Li7La3Zr2O12 Solid Electrolyte for Fast Lithium Ion Conduction. Sci. Rep 2015, 5 (1), 18053, DOI: 10.1038/srep1805336https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVWqtr%252FO&md5=e4662951940735540b7426b3987d7698Synergistic multi-doping effects on the Li7La3Zr2O12 solid electrolyte for fast lithium ion conductionShin, Dong Ok; Oh, Kyungbae; Kim, Kwang Man; Park, Kyu-Young; Lee, Byungju; Lee, Young-Gi; Kang, KisukScientific Reports (2015), 5 (), 18053CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)Here, we investigate the doping effects on the lithium ion transport behavior in garnet Li7La3Zr2O12 (LLZO) from the combined exptl. and theor. approach. The concn. of Li ion vacancy generated by the inclusion of aliovalent dopants such as Al3+ plays a key role in stabilizing the cubic LLZO. However, it is found that the site preference of Al in 24d position hinders the three dimensionally connected Li ion movement when heavily doped according to the structural refinement and the DFT calcns. In this report, we demonstrate that the multi-doping using addnl. Ta dopants into the Al-doped LLZO shifts the most energetically favorable sites of Al in the crystal structure from 24d to 96 h Li site, thereby providing more open space for Li ion transport. As a result of these synergistic effects, the multi-doped LLZO shows about three times higher ionic cond. of 6.14 × 10-4 S cm-1 than that of the singly-doped LLZO with a much less efforts in stabilizing cubic phases in the synthetic condition.
- 37Zhu, Y.; Connell, J. G.; Tepavcevic, S.; Zapol, P.; Garcia-Mendez, R.; Taylor, N. J.; Sakamoto, J.; Ingram, B. J.; Curtiss, L. A.; Freeland, J. W.; Fong, D. D.; Markovic, N. M. Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal. Adv. Energy Mater. 2019, 9 (12), 1803440, DOI: 10.1002/aenm.201803440There is no corresponding record for this reference.
- 38de Klerk, N. J. J.; Wagemaker, M. Diffusion Mechanism of the Sodium-Ion Solid Electrolyte Na3PS4 and Potential Improvements of Halogen Doping. Chem. Mater. 2016, 28 (9), 3122– 3130, DOI: 10.1021/acs.chemmater.6b0069838https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlvV2isLg%253D&md5=9ea12d404ba117dcd2be97c3bb80c8b4Diffusion Mechanism of the Sodium-Ion Solid Electrolyte Na3PS4 and Potential Improvements of Halogen Dopingde Klerk, Niek J. J.; Wagemaker, MarnixChemistry of Materials (2016), 28 (9), 3122-3130CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)D. functional theory (DFT) mol. dynamics (MD)-simulations were performed on cubic and tetragonal Na3PS4. The MD simulations show that the Na-cond. based on the predicted self-diffusion is high in both the cubic and tetragonal phases. Higher Na-ion cond. in Na3PS4 can be obtained by introducing Na-ion vacancies. Just 2% vacancies result in a cond. of 0.2 S/cm, which is an order of magnitude larger than the calcd. cond. of the stoichiometric compd. MD simulations of halogen-doped cubic Na3PS4 suggest a practical route to introduce vacancies, where Br-doping is predicted to result in the highest bulk cond. Detailed study of the Na-ion transitions during the MD simulation reveals the role of vacancies and phonons in the diffusion mechanism. Also, the orders of magnitude difference between the MD simulations and probably macroscopic cond. can should be significantly increased by reducing the grain boundary resistance.
- 39Walsh, A.; Sokol, A. A.; Catlow, C. R. A. Computational Approaches to Energy Materials; Wiley: Chichester, 2013.There is no corresponding record for this reference.
- 40Schleder, G. R.; Padilha, A. C. M.; Acosta, C. M.; Costa, M.; Fazzio, A. From DFT to Machine Learning: Recent Approaches to Materials Science-a Review. Journal of Physics: Materials 2019, 2 (3), 032001, DOI: 10.1088/2515-7639/ab084bThere is no corresponding record for this reference.
- 41Urban, A.; Seo, D.-H.; Ceder, G. Computational Understanding of Li-Ion Batteries. NPJ. Comput. Mater. 2016, 2 (1), 16002, DOI: 10.1038/npjcompumats.2016.241https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlslantL8%253D&md5=9ad3bdbb59d84c313b52507eb4f7cb0eComputational understanding of Li-ion batteriesUrban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrandnpj Computational Materials (2016), 2 (), 16002CODEN: NCMPCS; ISSN:2057-3960. (Nature Publishing Group)A review. Over the last two decades, computational methods have made tremendous advances, and today many key properties of lithium-ion batteries can be accurately predicted by first principles calcns. For this reason, computations have become a cornerstone of battery-related research by providing insight into fundamental processes that are not otherwise accessible, such as ionic diffusion mechanisms and electronic structure effects, as well as a quant. comparison with exptl. results. The aim of this review is to provide an overview of state-of-the-art ab initio approaches for the modeling of battery materials. We consider techniques for the computation of equil. cell voltages, 0-K and finite-temp. voltage profiles, ionic mobility and thermal and electrolyte stability. The strengths and weaknesses of different electronic structure methods, such as DFT+U and hybrid functionals, are discussed in the context of voltage and phase diagram predictions, and we review the merits of lattice models for the evaluation of finite-temp. thermodn. and kinetics. With such a complete set of methods at hand, first principles calcns. of ordered, cryst. solids, i.e., of most electrode materials and solid electrolytes, have become reliable and quant. However, the description of mol. materials and disordered or amorphous phases remains an important challenge. We highlight recent exciting progress in this area, esp. regarding the modeling of org. electrolytes and solid-electrolyte interfaces.
- 42Canepa, P. Pushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy Materials. ACS Materials Au 2023, 3 (2), 75– 82, DOI: 10.1021/acsmaterialsau.2c0005742https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisleitLvE&md5=5dfc732c1ff8ccea73679d959e1e1b7dPushing Forward Simulation Techniques of Ion Transport in Ion Conductors for Energy MaterialsCanepa, PieremanueleACS Materials Au (2023), 3 (2), 75-82CODEN: AMACGU; ISSN:2694-2461. (American Chemical Society)Simulation techniques are crucial to establish a firm link between phenomena occurring at the at. scale and macroscopic observations of functional materials. Importantly, extensive sampling of space and time scales is paramount to ensure good convergence of phys. relevant quantities to describe ion transport in energy materials. Here, a no. of simulation methods to address ion transport in energy materials are discussed, with the pros and cons of each methodol. put forward. Emphasis is given to the stochastic nature of results produced by kinetic Monte Carlo, which can adequately account for compositional disorder across multiple sublattices in solids.
- 43Huang, B.; von Rudorff, G. F.; von Lilienfeld, O. A. The Central Role of Density Functional Theory in the AI Age. Science (1979) 2023, 381 (6654), 170– 175, DOI: 10.1126/science.abn3445There is no corresponding record for this reference.
- 44Kresse, G.; Furthmüller, J. Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Comput. Mater. Sci. 1996, 6, 15, DOI: 10.1016/0927-0256(96)00008-044https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28XmtFWgsrk%253D&md5=779b9a71bbd32904f968e39f39946190Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis setKresse, G.; Furthmuller, J.Computational Materials Science (1996), 6 (1), 15-50CODEN: CMMSEM; ISSN:0927-0256. (Elsevier)The authors present a detailed description and comparison of algorithms for performing ab-initio quantum-mech. calcns. using pseudopotentials and a plane-wave basis set. The authors will discuss: (a) partial occupancies within the framework of the linear tetrahedron method and the finite temp. d.-functional theory, (b) iterative methods for the diagonalization of the Kohn-Sham Hamiltonian and a discussion of an efficient iterative method based on the ideas of Pulay's residual minimization, which is close to an order N2atoms scaling even for relatively large systems, (c) efficient Broyden-like and Pulay-like mixing methods for the charge d. including a new special preconditioning optimized for a plane-wave basis set, (d) conjugate gradient methods for minimizing the electronic free energy with respect to all degrees of freedom simultaneously. The authors have implemented these algorithms within a powerful package called VAMP (Vienna ab-initio mol.-dynamics package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semi-conducting surfaces, phonons in simple metals, transition metals and semiconductors) and turned out to be very reliable.
- 45Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54 (16), 11169– 11186, DOI: 10.1103/PhysRevB.54.1116945https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK28Xms1Whu7Y%253D&md5=9c8f6f298fe5ffe37c2589d3f970a697Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis setKresse, G.; Furthmueller, J.Physical Review B: Condensed Matter (1996), 54 (16), 11169-11186CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)The authors present an efficient scheme for calcg. the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrixes will be discussed. This approach is stable, reliable, and minimizes the no. of order Natoms3 operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special "metric" and a special "preconditioning" optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calcns. It will be shown that the no. of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order Natoms2 scaling is found for systems contg. up to 1000 electrons. If we take into account that the no. of k points can be decreased linearly with the system size, the overall scaling can approach Natoms. They have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large no. of different systems (liq. and amorphous semiconductors, liq. simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable.
- 46Senftle, T. P.; Hong, S.; Islam, M. M.; Kylasa, S. B.; Zheng, Y.; Shin, Y. K.; Junkermeier, C.; Engel-Herbert, R.; Janik, M. J.; Aktulga, H. M.; Verstraelen, T.; Grama, A.; van Duin, A. C. T. The ReaxFF Reactive Force-Field: Development, Applications and Future Directions. NPJ. Comput. Mater. 2016, 2 (1), 15011, DOI: 10.1038/npjcompumats.2015.1146https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlslantL4%253D&md5=ee5492fa7acb1ac6bbe6cba438128c20The ReaxFF reactive force-field: development, applications and future directionsSenftle, Thomas P.; Hong, Sungwook; Islam, Md. Mahbubul; Kylasa, Sudhir B.; Zheng, Yuanxia; Shin, Yun Kyung; Junkermeier, Chad; Engel-Herbert, Roman; Janik, Michael J.; Aktulga, Hasan Metin; Verstraelen, Toon; Grama, Ananth; van Duin, Adri C. T.npj Computational Materials (2016), 2 (), 15011CODEN: NCMPCS; ISSN:2057-3960. (Nature Publishing Group)The reactive force-field (ReaxFF) interat. potential is a powerful computational tool for exploring, developing and optimizing material properties. Methods based on the principles of quantum mechanics (QM), while offering valuable theor. guidance at the electronic level, are often too computationally intense for simulations that consider the full dynamic evolution of a system. Alternatively, empirical interat. potentials that are based on classical principles require significantly fewer computational resources, which enables simulations to better describe dynamic processes over longer timeframes and on larger scales. Such methods, however, typically require a predefined connectivity between atoms, precluding simulations that involve reactive events. The ReaxFF method was developed to help bridge this gap. Approaching the gap from the classical side, ReaxFF casts the empirical interat. potential within a bond-order formalism, thus implicitly describing chem. bonding without expensive QM calcns. This article provides an overview of the development, application, and future directions of the ReaxFF method.
- 47Harrison, J. A.; Schall, J. D.; Maskey, S.; Mikulski, P. T.; Knippenberg, M. T.; Morrow, B. H. Review of Force Fields and Intermolecular Potentials Used in Atomistic Computational Materials Research. Appl. Phys. Rev. 2018, 5 (3), 031104, DOI: 10.1063/1.502080847https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsF2gurvN&md5=1b14331bd7cc33a4bf38a8481acc21c1Review of force fields and intermolecular potentials used in atomistic computational materials researchHarrison, Judith A.; Schall, J. David; Maskey, Sabina; Mikulski, Paul T.; Knippenberg, M. Todd; Morrow, Brian H.Applied Physics Reviews (2018), 5 (3), 031104/1-031104/24CODEN: APRPG5; ISSN:1931-9401. (American Institute of Physics)A review. Mol. simulation is a powerful computational tool for a broad range of applications including the examn. of materials properties and accelerating drug discovery. At the heart of mol. simulation is the analytic potential energy function. These functions span the range of complexity from very simple functions used to model generic phenomena to complex functions designed to model chem. reactions. The complexity of the math. function impacts the computational speed and is typically linked to the accuracy of the results obtained from simulations that utilize the function. One approach to improving accuracy is to simply add more parameters and addnl. complexity to the analytic function. This approach is typically used in non-reactive force fields where the functional form is not derived from quantum mech. principles. The form of other types of potentials, such as the bond-order potentials, is based on quantum mechanics and has led to varying levels of accuracy and transferability. When selecting a potential energy function for use in mol. simulations, the accuracy, transferability, and computational speed must all be considered. In this focused review, some of the more commonly used potential energy functions for mol. simulations are reviewed with an eye toward presenting their general forms, strengths, and weaknesses. (c) 2018 American Institute of Physics.
- 48Müser, M. H.; Sukhomlinov, S. V.; Pastewka, L. Interatomic Potentials: Achievements and Challenges. Adv. Phys. X 2023, 8 (1), 2093129, DOI: 10.1080/23746149.2022.2093129There is no corresponding record for this reference.
- 49Pedone, A.; Malavasi, G.; Menziani, M. C.; Cormack, A. N.; Segre, U. A New Self-Consistent Empirical Interatomic Potential Model for Oxides, Silicates, and Silica-Based Glasses. J. Phys. Chem. B 2006, 110 (24), 11780– 11795, DOI: 10.1021/jp061101849https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XltVCgu7c%253D&md5=e282f713a1dda5cbb5805f60090cd9fcA New Self-Consistent Empirical Interatomic Potential Model for Oxides, Silicates, and Silica-Based GlassesPedone, Alfonso; Malavasi, Gianluca; Menziani, M. Cristina; Cormack, Alastair N.; Segre, UldericoJournal of Physical Chemistry B (2006), 110 (24), 11780-11795CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)A new empirical pairwise potential model for ionic and semi-ionic oxides has been developed. Its transferability and reliability have been demonstrated by testing the potentials toward the prediction of structural and mech. properties of a wide range of silicates of technol. and geol. importance. The partial ionic charge model with a Morse function is used, and it allows the modeling of the quenching of melts, silicate glasses, and inorg. crystals at high-pressure and high-temp. conditions. The results obtained by mol. dynamics and free energy calcns. are discussed in relation to the prediction of structural and mech. properties of a series of soda lime silicate glasses.
- 50Jalem, R.; Rushton, M. J. D.; Manalastas, W.; Nakayama, M.; Kasuga, T.; Kilner, J. A.; Grimes, R. W. Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid Electrolytes. Chem. Mater. 2015, 27 (8), 2821– 2831, DOI: 10.1021/cm504512250https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXlvV2itLw%253D&md5=f01c2f4d22f12f5e87917b82a4ce3f59Effects of Gallium Doping in Garnet-Type Li7La3Zr2O12 Solid ElectrolytesJalem, Randy; Rushton, M. J. D.; Manalastas, William; Nakayama, Masanobu; Kasuga, Toshihiro; Kilner, John A.; Grimes, Robin W.Chemistry of Materials (2015), 27 (8), 2821-2831CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Garnet-type Li7La3Zr2O12 (LLZrO) is a candidate solid electrolyte material that is now being intensively optimized for application in com. competitive solid state Li+ ion batteries. In this study we investigate, by force-field-based simulations, the effects of Ga3+ doping in LLZrO. We confirm the stabilizing effect of Ga3+ on the cubic phase. We also det. that Ga3+ addn. does not lead to any appreciable structural distortion. Li site connectivity is not significantly deteriorated by the Ga3+ addn. (>90% connectivity retained up to x = 0.30 in Li7-3xGaxLa3Zr2O12). Interestingly, two compositional regions are predicted for bulk Li+ ion cond. in the cubic phase: (i) a decreasing trend for 0 ≤ x ≤ 0.10 and (ii) a relatively flat trend for 0.10 < x ≤ 0.30. This cond. behavior is explained by combining analyses using percolation theory, van Hove space time correlation, the radial distribution function, and trajectory d.
- 51Kim, J.-S.; Jung, W. D.; Son, J.-W.; Lee, J.-H.; Kim, B.-K.; Chung, K.-Y.; Jung, H.-G.; Kim, H. Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium Thiophosphates. ACS Appl. Mater. Interfaces 2019, 11 (1), 13– 18, DOI: 10.1021/acsami.8b1752451https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFyrsr%252FP&md5=8521e7817fa4fc157cb5700dcfba1bf3Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium ThiophosphatesKim, Ji-Su; Jung, Wo Dum; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Chung, Kyung-Yoon; Jung, Hun-Gi; Kim, HyoungchulACS Applied Materials & Interfaces (2019), 11 (1), 13-18CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)The authors detd. the interat. potentials of the Li-[PS43-] building block in (Li2S)0.75(P2S5)0.25 (LPS) and predicted the Li-ion cond. (σLi) of glass-ceramic LPS from mol. dynamics. The Li-ion conduction characteristics in the cryst./interfacial/glassy structure were decompd. by considering the structural ordering differences. The superior σLi of the glassy LPS could be attributed to the fact that ∼40% of its structure consists of the short-ranged cubic S-sublattice instead of the hcp. γ-phase. This glassy LPS has a σLi of 4.08 × 10-1 mS/cm, an improvement of ∼100 times relative to that of the γ-phase, which is in agreement with the expts.
- 52Dawson, J. A.; Islam, M. S. A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li10GeP2S12 Solid Electrolyte. ACS Mater. Lett. 2022, 4 (2), 424– 431, DOI: 10.1021/acsmaterialslett.1c0076652https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFSltLk%253D&md5=f12633443acbe9935f46a5f07d943641A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li10GeP2S12 Solid ElectrolyteDawson, James A.; Islam, M. SaifulACS Materials Letters (2022), 4 (2), 424-431CODEN: AMLCEF; ISSN:2639-4979. (American Chemical Society)The discovery of the lithium superionic conductor Li10GeP2S12 (LGPS) has led to significant research activity on solid electrolytes for high-performance solid-state batteries. Despite LGPS exhibiting a remarkably high room-temp. Li-ion cond., comparable to that of the liq. electrolytes used in current Li-ion batteries, nanoscale effects in this material have not been fully explored. Here, we predict that nanosizing of LGPS can be used to further enhance its Li-ion cond. By utilizing state-of-the-art nanoscale modeling techniques, our results reveal significant nanosizing effects with the Li-ion cond. of LGPS increasing with decreasing particle vol. These features are due to a fundamental change from a primarily one-dimensional Li-ion conduction mechanism to a three-dimensional mechanism and major changes in the local structure. For the smallest nanometric particle size, the Li-ion cond. at room temp. is three times higher than that of the bulk system. These findings reveal that nanosizing LGPS and related solid electrolytes could be an effective design approach to enhance their Li-ion cond.
- 53Kim, K.; Dive, A.; Grieder, A.; Adelstein, N.; Kang, S.; Wan, L. F.; Wood, B. C. Flexible Machine-Learning Interatomic Potential for Simulating Structural Disordering Behavior of Li7La3Zr2O12 Solid Electrolytes. J. Chem. Phys. 2022, 156 (22), 221101, DOI: 10.1063/5.009034153https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhsFektbnI&md5=0a496d54e76df8902bb3b22463813ad5Flexible machine-learning interatomic potential for simulating structural disordering behavior of Li7La3Zr2O12 solid electrolytesKim, Kwangnam; Dive, Aniruddha; Grieder, Andrew; Adelstein, Nicole; Kang, ShinYoung; Wan, Liwen F.; Wood, Brandon C.Journal of Chemical Physics (2022), 156 (22), 221101CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)Batteries based on solid-state electrolytes, including Li7La3Zr2O12 (LLZO), promise improved safety and increased energy d.; however, at. disorder at grain boundaries and phase boundaries can severely deteriorate their performance. Machine-learning (ML) interat. potentials offer a uniquely compelling soln. for simulating chem. processes, rare events, and phase transitions assocd. with these complex interfaces by mixing high scalability with quantum-level accuracy, provided that they can be trained to properly address at. disorder. To this end, we report the construction and validation of an ML potential that is specifically designed to simulate cryst., disordered, and amorphous LLZO systems across a wide range of conditions. The ML model is based on a neural network algorithm and is trained using ab initio data. Performance tests prove that the developed ML potential can predict accurate structural and vibrational characteristics, elastic properties, and Li diffusivity of LLZO comparable to ab initio simulations. As a demonstration of its applicability to larger systems, we show that the potential can correctly capture grain boundary effects on diffusivity, as well as the thermal transition behavior of LLZO. These examples show that the ML potential enables simulations of transitions between well-defined and disordered structures with quantum-level accuracy at speeds thousands of times faster than ab initio methods. (c) 2022 American Institute of Physics.
- 54Lee, T.; Qi, J.; Gadre, C. A.; Huyan, H.; Ko, S.-T.; Zuo, Y.; Du, C.; Li, J.; Aoki, T.; Wu, R.; Luo, J.; Ong, S. P.; Pan, X. Atomic-Scale Origin of the Low Grain-Boundary Resistance in Perovskite Solid Electrolyte Li0.375Sr0.4375Ta0.75Zr0.25O3. Nat. Commun. 2023, 14 (1), 1940, DOI: 10.1038/s41467-023-37115-654https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXnt1Gjt7o%253D&md5=f3d5e45e57b160135f0570bf855ce40fAtomic-scale origin of the low grain-boundary resistance in perovskite solid electrolyte Li0.375Sr0.4375Ta0.75Zr0.25O3Lee, Tom; Qi, Ji; Gadre, Chaitanya A.; Huyan, Huaixun; Ko, Shu-Ting; Zuo, Yunxing; Du, Chaojie; Li, Jie; Aoki, Toshihiro; Wu, Ruqian; Luo, Jian; Ong, Shyue Ping; Pan, XiaoqingNature Communications (2023), 14 (1), 1940CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Oxide solid electrolytes (OSEs) have the potential to achieve improved safety and energy d. for lithium-ion batteries, but their high grain-boundary (GB) resistance generally is a bottleneck. In the well-studied perovskite oxide solid electrolyte, Li3xLa2/3-xTiO3 (LLTO), the ionic cond. of grain boundaries is about three orders of magnitude lower than that of the bulk. In contrast, the related Li0.375Sr0.4375Ta0.75Zr0.25O3 (LSTZ0.75) perovskite exhibits low grain boundary resistance for reasons yet unknown. Here, we use aberration-cor. scanning transmission electron microscopy and spectroscopy, along with an active learning moment tensor potential, to reveal the at. scale structure and compn. of LSTZ0.75 grain boundaries. Vibrational electron energy loss spectroscopy is applied for the first time to reveal atomically resolved vibrations at grain boundaries of LSTZ0.75 and to characterize the otherwise unmeasurable Li distribution therein. We find that Li depletion, which is a major reason for the low grain boundary ionic cond. of LLTO, is absent for the grain boundaries of LSTZ0.75. Instead, the low grain boundary resistivity of LSTZ0.75 is attributed to the formation of a nanoscale defective cubic perovskite interfacial structure that contained abundant vacancies. Our study provides new insights into the at. scale mechanisms of low grain boundary resistivity.
- 55Krenzer, G.; Klarbring, J.; Tolborg, K.; Rossignol, H.; McCluskey, A. R.; Morgan, B. J.; Walsh, A. Nature of the Superionic Phase Transition of Lithium Nitride from Machine Learning Force Fields. Chem. Mater. 2023, 35 (15), 6133– 6140, DOI: 10.1021/acs.chemmater.3c0127155https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsV2ltbnO&md5=7d6ce15d243dab3a98c9db3e76e07945Nature of the Superionic Phase Transition of Lithium Nitride from Machine Learning Force FieldsKrenzer, Gabriel; Klarbring, Johan; Tolborg, Kasper; Rossignol, Hugo; McCluskey, Andrew R.; Morgan, Benjamin J.; Walsh, AronChemistry of Materials (2023), 35 (15), 6133-6140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Superionic conductors have great potential as solid-state electrolytes, but the physics of type-II superionic transitions remains elusive. In this study, we employed mol. dynamics simulations, using machine learning force fields, to investigate the type-II superionic phase transition in α-Li3N. We characterized Li3N above and below the superionic phase transition by calcg. the heat capacity, Li+ ion self-diffusion coeff., and Li defect concns. as functions of temp. Our findings indicate that both the Li+ self-diffusion coeff. and Li vacancy concn. follow distinct Arrhenius relationships in the normal and superionic regimes. The activation energies for self-diffusion and Li vacancy formation decrease by a similar proportion across the superionic phase transition. This result suggests that the superionic transition may be driven by a decrease in defect formation energetics rather than changes in Li transport mechanism. This insight may have implications for other type-II superionic materials.
- 56Mueller, T.; Hernandez, A.; Wang, C. Machine Learning for Interatomic Potential Models. J. Chem. Phys. 2020, 152 (5), 050902, DOI: 10.1063/1.512633656https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXisV2gurY%253D&md5=a9a8b282be7a0356715e8aab2e207347Machine learning for interatomic potential modelsMueller, Tim; Hernandez, Alberto; Wang, ChuhongJournal of Chemical Physics (2020), 152 (5), 050902CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)A review. The use of supervised machine learning to develop fast and accurate interat. potential models is transforming mol. and materials research by greatly accelerating at.-scale simulations with little loss of accuracy. Three years ago, Jorg Behler published a perspective in this journal providing an overview of some of the leading methods in this field. In this perspective, we provide an updated discussion of recent developments, emerging trends, and promising areas for future research in this field. We include in this discussion an overview of three emerging approaches to developing machine-learned interat. potential models that have not been extensively discussed in existing reviews: moment tensor potentials, message-passing networks, and symbolic regression. (c) 2020 American Institute of Physics.
- 57Unke, O. T.; Chmiela, S.; Sauceda, H. E.; Gastegger, M.; Poltavsky, I.; Schütt, K. T.; Tkatchenko, A.; Müller, K.-R. Machine Learning Force Fields. Chem. Rev. 2021, 121 (16), 10142– 10186, DOI: 10.1021/acs.chemrev.0c0111157https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmtVOksL0%253D&md5=8a40dd8c5c642c22f40628f2b1ba22e9Machine Learning Force FieldsUnke, Oliver T.; Chmiela, Stefan; Sauceda, Huziel E.; Gastegger, Michael; Poltavsky, Igor; Schuett, Kristof T.; Tkatchenko, Alexandre; Mueller, Klaus-RobertChemical Reviews (Washington, DC, United States) (2021), 121 (16), 10142-10186CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. In recent years, the use of machine learning (ML) in computational chem. has enabled numerous advances previously out of reach due to the computational complexity of traditional electronic-structure methods. One of the most promising applications is the construction of ML-based force fields (FFs), with the aim to narrow the gap between the accuracy of ab initio methods and the efficiency of classical FFs. The key idea is to learn the statistical relation between chem. structure and potential energy without relying on a preconceived notion of fixed chem. bonds or knowledge about the relevant interactions. Such universal ML approxns. are in principle only limited by the quality and quantity of the ref. data used to train them. This review gives an overview of applications of ML-FFs and the chem. insights that can be obtained from them. The core concepts underlying ML-FFs are described in detail, and a step-by-step guide for constructing and testing them from scratch is given. The text concludes with a discussion of the challenges that remain to be overcome by the next generation of ML-FFs.
- 58Zuo, Y.; Chen, C.; Li, X.; Deng, Z.; Chen, Y.; Behler, J.; Csányi, G.; Shapeev, A. V.; Thompson, A. P.; Wood, M. A.; Ong, S. P. Performance and Cost Assessment of Machine Learning Interatomic Potentials. J. Phys. Chem. A 2020, 124 (4), 731– 745, DOI: 10.1021/acs.jpca.9b0872358https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXmtVKjsg%253D%253D&md5=7716fe55d3269109bfc101fdfc25d823Performance and Cost Assessment of Machine Learning Interatomic PotentialsZuo, Yunxing; Chen, Chi; Li, Xiangguo; Deng, Zhi; Chen, Yiming; Behler, Jorg; Csanyi, Gabor; Shapeev, Alexander V.; Thompson, Aidan P.; Wood, Mitchell A.; Ong, Shyue PingJournal of Physical Chemistry A (2020), 124 (4), 731-745CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)Machine learning of the quant. relationship between local environment descriptors and the potential energy surface of a system of atoms has emerged as a new frontier in the development of interat. potentials (IAPs). Here, we present a comprehensive evaluation of machine learning IAPs (ML-IAPs) based on four local environment descriptors-atom-centered symmetry functions (ACSF), smooth overlap of at. positions (SOAP), the spectral neighbor anal. potential (SNAP) bispectrum components, and moment tensors-using a diverse data set generated using high-throughput d. functional theory (DFT) calcns. The data set comprising bcc (Li, Mo) and fcc (Cu, Ni) metals and diamond group IV semiconductors (Si, Ge) is chosen to span a range of crystal structures and bonding. All descriptors studied show excellent performance in predicting energies and forces far surpassing that of classical IAPs, as well as predicting properties such as elastic consts. and phonon dispersion curves. We observe a general trade-off between accuracy and the degrees of freedom of each model and, consequently, computational cost. We will discuss these trade-offs in the context of model selection for mol. dynamics and other applications.
- 59Thompson, A. P.; Aktulga, H. M.; Berger, R.; Bolintineanu, D. S.; Brown, W. M.; Crozier, P. S.; in ’t Veld, P. J.; Kohlmeyer, A.; Moore, S. G.; Nguyen, T. D.; Shan, R.; Stevens, M. J.; Tranchida, J.; Trott, C.; Plimpton, S. J. LAMMPS - a Flexible Simulation Tool for Particle-Based Materials Modeling at the Atomic, Meso, and Continuum Scales. Comput. Phys. Commun. 2022, 271, 108171, DOI: 10.1016/j.cpc.2021.10817159https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlSrsb7O&md5=cd0bfd050820e97c11779003add20ed3LAMMPS - a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scalesThompson, Aidan P.; Aktulga, H. Metin; Berger, Richard; Bolintineanu, Dan S.; Brown, W. Michael; Crozier, Paul S.; in 't Veld, Pieter J.; Kohlmeyer, Axel; Moore, Stan G.; Nguyen, Trung Dac; Shan, Ray; Stevens, Mark J.; Tranchida, Julien; Trott, Christian; Plimpton, Steven J.Computer Physics Communications (2022), 271 (), 108171CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)Since the classical mol. dynamics simulator LAMMPS was released as an open source code in 2004, it has become a widely-used tool for particle-based modeling of materials at length scales ranging from at. to mesoscale to continuum. Reasons for its popularity are that it provides a wide variety of particle interaction models for different materials, that it runs on any platform from a single CPU core to the largest supercomputers with accelerators, and that it gives users control over simulation details, either via the input script or by adding code for new interat. potentials, constraints, diagnostics, or other features needed for their models. As a result, hundreds of people have contributed new capabilities to LAMMPS and it has grown from fifty thousand lines of code in 2004 to a million lines today. In this paper several of the fundamental algorithms used in LAMMPS are described along with the design strategies which have made it flexible for both users and developers. We also highlight some capabilities recently added to the code which were enabled by this flexibility, including dynamic load balancing, on-the-fly visualization, magnetic spin dynamics models, and quantum-accuracy machine learning interat. potentials.Program Title: Large-scale Atomic/Mol. Massively Parallel Simulator (LAMMPS)CPC Library link to program files:https://doi.org/10.17632/cxbxs9btsv.1Developer's repository link:https://github.com/lammps/lammpsLicensing provisions: GPLv2Programming language: C++, Python, C, FortranSupplementary material:https://www.lammps.orgNature of problem: Many science applications in physics, chem., materials science, and related fields require parallel, scalable, and efficient generation of long, stable classical particle dynamics trajectories. Within this common problem definition, there lies a great diversity of use cases, distinguished by different particle interaction models, external constraints, as well as timescales and lengthscales ranging from at. to mesoscale to macroscopic.Soln. method: The LAMMPS code uses parallel spatial decompn., distributed neighbor lists, and parallel FFTs for long-range Coulombic interactions [1]. The time integration algorithm is based on the Stormer-Verlet symplectic integrator [2], which provides better stability than higher-order non-symplectic methods. In addn., LAMMPS supports a wide range of interat. potentials, constraints, diagnostics, software interfaces, and pre- and post-processing features.Addnl. comments including restrictions and unusual features: This paper serves as the definitive ref. for the LAMMPS code.S. Plimpton, Fast parallel algorithms for short-range mol. dynamics. Phys. 117 (1995) 1-19.L. Verlet, Computer expts. on classical fluids: I. Thermodynamical properties of Lennard-Jones mols., Phys. Rev. 159 (1967) 98-103.
- 60Hirel, P. Atomsk: A Tool for Manipulating and Converting Atomic Data Files. Comput. Phys. Commun. 2015, 197, 212– 219, DOI: 10.1016/j.cpc.2015.07.01260https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlSlt7rP&md5=7869db03e79a37285988e2db890a9ce1Atomsk: A tool for manipulating and converting atomic data filesHirel, PierreComputer Physics Communications (2015), 197 (), 212-219CODEN: CPHCBZ; ISSN:0010-4655. (Elsevier B.V.)We present a libre, Open Source command-line program named Atomsk, that aims at creating and manipulating at. systems for the purposes of ab initio calcns., classical atomistic calcns., and visualization, in the areas of computational physics and chem. The program can run on GNU/Linux, Apple Mac OS X, and Microsoft Windows platforms. Many file formats are supported, allowing for easy conversion of at. configuration files. The command-line options allow to construct supercells, insert point defects (vacancies, interstitials), line defects (dislocations, cracks), plane defects (stacking faults), as well as other transformations. Several options can be applied consecutively, allowing for a comprehensive workflow from a unit cell to the final at. system. Some modes allow to construct complex structures, or to perform specific anal. of at. systems.
- 61Yu, S.; Siegel, D. J. Grain Boundary Contributions to Li-Ion Transport in the Solid Electrolyte Li7La3Zr2O12 (LLZO). Chem. Mater. 2017, 29 (22), 9639– 9647, DOI: 10.1021/acs.chemmater.7b0280561https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslSisbvO&md5=5546c0f2ab692c15abbe0ad785445b76Grain Boundary Contributions to Li-Ion Transport in the Solid Electrolyte Li7La3Zr2O12 (LLZO)Yu, Seungho; Siegel, Donald J.Chemistry of Materials (2017), 29 (22), 9639-9647CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The oxide with nominal compn. Li7La3Zr2O12 (LLZO) is a promising solid electrolyte thanks to its high (bulk) Li-ion cond., negligible electronic transport, chem. stability against Li metal, and wide electrochem. window. Despite these promising characteristics, recent measurements suggest that microstructural features, specifically, grain boundaries (GBs), contribute to undesirable short-circuiting and resistance in polycryst. LLZO membranes. Toward the goal of understanding GB-related phenomena, the present study characterizes the energetics, compn., and transport properties of three low-energy (S3 and S5) sym. tilt GBs in LLZO at the at. scale. Monte Carlo simulations reveal that the GB planes are enriched with Li, and to a lesser extent with oxygen. Mol. dynamics simulations on these off-stoichiometric boundaries were used to assess Li-ion transport within and across the boundary planes. We find that Li transport is generally reduced in the GB region; however, the magnitude of this effect is sensitive to temp. and GB structure. Li-ion diffusion is comparable in all three GBs at the high temps. encountered during processing, and only 2-3 times slower than bulk diffusion. These similarities vanish at room temp., where diffusion in the more compact S3 boundary remains relatively fast (half the bulk rate), while transport in the S5 boundaries is roughly 2 orders of magnitude slower. These trends mirror the activation energies for diffusion, which in the S5 boundaries are up to 35% larger than in bulk LLZO, and are identical to the bulk in the S3 boundary. Diffusion within the S5 boundaries is obsd. to be isotropic. In contrast, intraplane diffusion in the S3 boundary plane at room temp. is predicted to exceed that of the bulk, while transboundary diffusion is ∼200 times slower than that in the bulk. Our observation of mixed GB transport contributions (some boundaries support fast diffusion, while others are slow) is consistent with the limited GB resistance obsd. in polycryst. LLZO samples processed at high temps. These data also suggest that higher-energy GBs with less-compact structures should penalize Li-ion cond. to a greater degree.
- 62Chen, B.; Xu, C.; Zhou, J. Insights into Grain Boundary in Lithium-Rich Anti-Perovskite as Solid Electrolytes. J. Electrochem. Soc. 2018, 165 (16), A3946– A3951, DOI: 10.1149/2.0831816jes62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjs1emsbc%253D&md5=1a5902b2f9485e7167bccf1fda185812Insights into grain boundary in lithium-rich anti-perovskite as solid electrolytesChen, Bingbing; Xu, Chaoqun; Zhou, JianqiuJournal of the Electrochemical Society (2018), 165 (16), A3946-A3951CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)In all-solid-state Li batteries, antiperovskite solid electrolyte has high ionic cond. and high stability with Li metal anode. However, grain boundaries (GBs) contribute to undesirable resistance limiting ionic cond. in antiperovskite, and there is limited knowledge about the GBs in solid electrolyte, particularly at the at. scale. Here, using d. functional theory calcns. 4 sym tilt (Σ3 and Σ5) GBs effects on structural characteristics and ions transport in antiperovskite (Li3OCl) solid electrolyte. Using 1st-principles simulation, GBs are relatively stable resulting in its high concns. in Li3OCl. The presence of GBs can improve compatibility with electrode, while it decreases the ionic cond. and band gaps in Li3OCl. Also, the Σ5 GBs structures are softer and higher ionic cond. than Σ3 GBs, delivering a new insight that GBs types may importantly affect the softness and ionic cond. in solid electrolyte. Significantly, the easiest Li ion migration pathway is along GB direction in Li3OCl with GBs structures. The present work uncovers the GBs behaviors in antiperovskite solid electrolyte, which can help one to guide the design of high performance antiperovskite solid electrolyte.
- 63Lee, H. J.; Darminto, B.; Narayanan, S.; Diaz-Lopez, M.; Xiao, A. W.; Chart, Y.; Lee, J. H.; Dawson, J. A.; Pasta, M. Li-Ion Conductivity in Li2OHCl1-xBrx Solid Electrolytes: Grains, Grain Boundaries and Interfaces. J. Mater. Chem. A 2022, 10 (21), 11574– 11586, DOI: 10.1039/D2TA01462A63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1Cltb7L&md5=6182880e89321977415bf61e1dc3b89cLi-ion conductivity in Li2OHCl1-xBrx solid electrolytes: grains, grain boundaries and interfacesLee, Hyeon Jeong; Darminto, Brigita; Narayanan, Sudarshan; Diaz-Lopez, Maria; Xiao, Albert W.; Chart, Yvonne; Lee, Ji Hoon; Dawson, James A.; Pasta, MauroJournal of Materials Chemistry A: Materials for Energy and Sustainability (2022), 10 (21), 11574-11586CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)In this study, we conduct a comprehensive investigation of the effect of grain, grain boundary and interfacial resistance on the total Li-ion cond. in Li2OHCl1-xBrx antiperovskite solid electrolytes. We highlight how the thermal expansion coeff. can serve as an indicator for the presence of structural defects, which are difficult to probe directly with X-ray techniques, and their effect on bulk Li-ion conduction. The detrimental effect of grain boundaries on ionic cond. is investigated by atomistic calcns. and validated exptl. by electrochem. impedance spectroscopy on pellets with controlled grain size. The effect of compn. on interfacial resistance is probed by electrochem. impedance spectroscopy and XPS. These insights provide design principles to improve Li-ion cond. in lithium hydroxide halide antiperovskites.
- 64Van Duong, L.; Nguyen, M. T.; Zulueta, Y. A. Unravelling the Alkali Transport Properties in Nanocrystalline A3OX (A = Li, Na, X = Cl, Br) Solid State Electrolytes. A Theoretical Prediction. RSC Adv. 2022, 12 (31), 20029– 20036, DOI: 10.1039/D2RA03370D64https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhslGgur3L&md5=c9ebf92bdaa71571c5c39f48d19b795dUnravelling the alkali transport properties in nanocrystalline A3OX (A = Li, Na, X = Cl, Br) solid state electrolytes. A theoretical predictionVan Duong, Long; Nguyen, Minh Tho; Zulueta, Yohandys A.RSC Advances (2022), 12 (31), 20029-20036CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Transport properties of the halogeno-alkali oxides A3OX (A = Li, Na, X = Cl, Br) nanocryst. samples with the presence of .sum.3(111) grain boundaries were computed using large-scale mol. dynamic simulations. Results on the diffusion/conduction process show that these nanocryst. samples are characterized with higher activation energies as compared to previous theor. studies, but closer to expt. Such a performance can be attributed to the larger at. d. at the .sum.3(111) grain boundary regions within the nanocrystals. Despite a minor deterioration of transport properties of the mixed cation Li2NaOX and Na2LiOX samples, these halogeno-alkali oxides can also be considered as good inorg. solid electrolytes in both Li- and Na-ion batteries.
- 65Dawson, J. A.; Famprikis, T.; Johnston, K. E. Anti-Perovskites for Solid-State Batteries: Recent Developments, Current Challenges and Future Prospects. J. Mater. Chem. A Mater. 2021, 9 (35), 18746– 18772, DOI: 10.1039/D1TA03680G65https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVylur%252FK&md5=f2f94c55a221b143804268510b7d865aAnti-perovskites for solid-state batteries: recent developments, current challenges and future prospectsDawson, James A.; Famprikis, Theodosios; Johnston, Karen E.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (35), 18746-18772CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A review. Current com. batteries cannot meet the requirements of next-generation technologies, meaning that the creation of new high-performance batteries at low cost is essential for the electrification of transport and large-scale energy storage. Solid-state batteries are being widely anticipated to lead to a step improvement in the performance and safety of batteries and their success is heavily dependent on the discovery, design and optimization of the solid electrolytes that they are based on. In recent years, Li- and Na-rich anti-perovskite solid electrolytes have risen to become highly promising candidate materials for solid-state batteries on the basis of their high ionic cond., wide electrochem. window, stability, low cost and structural diversity. This perspective highlights exptl. and atomistic modeling progress currently being made for Li- and Na-rich anti-perovskite solid electrolytes. We focus on several crit. areas of interest in these materials, including synthesisability, structure, ion transport mechanisms, anion rotation, interfaces and their compatibility with anti-perovskite cathodes for the possible formation of anti-perovskite electrolyte- and cathode-based solid-state batteries. The opportunities and challenges for the design and utilization of these materials in state-of-the-art solid-state batteries are also discussed. As featured throughout this perspective, the versatility, diversity and performance of anti-perovskite solid electrolytes make them one of the most important materials families currently under consideration for solid-state batteries.
- 66Dawson, J. A.; Attari, T. S.; Chen, H.; Emge, S. P.; Johnston, K. E.; Islam, M. S. Elucidating Lithium-Ion and Proton Dynamics in Anti-Perovskite Solid Electrolytes. Energy Environ. Sci. 2018, 11 (10), 2993– 3002, DOI: 10.1039/C8EE00779A66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVSqs7bP&md5=1a9ea4bb0f4d83f74082c1130d605bb7Elucidating lithium-ion and proton dynamics in anti-perovskite solid electrolytesDawson, James A.; Attari, Tavleen S.; Chen, Hungru; Emge, Steffen P.; Johnston, Karen E.; Islam, M. SaifulEnergy & Environmental Science (2018), 11 (10), 2993-3002CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)All-solid-state Li-ion batteries are currently attracting considerable research attention as they present a viable opportunity for increased energy d. and safety when compared to conventional liq. electrolyte-based devices. The Li-rich anti-perovskite Li3-xOHxCl has generated recent interest as a potential solid electrolyte material, but its lithium and proton transport capabilities as a function of compn. are not fully characterized. In this work, we apply a combination of ab initio mol. dynamics and 1H, 2H and 7Li solid-state NMR spectroscopy to study the mobility of lithium ions and protons in Li3-xOHxCl. Our calcns. predict a strongly exothermic hydration enthalpy for Li3OCl, which explains the ease with which this material absorbs moisture and the difficulty in synthesizing moisture-free samples. We show that the activation energy for Li-ion conduction increases with increasing proton content. The atomistic simulations indicate fast Li-ion diffusion but rule out the contribution of long-range proton diffusion. These findings are supported by variable-temp. solid-state NMR expts., which indicate localized proton motion and long-range Li-ion mobility that are intimately connected. Our findings confirm that Li3-xOHxCl is a promising solid electrolyte material for all-solid-state Li-ion batteries.
- 67Sun, Y.; Wang, Y.; Liang, X.; Xia, Y.; Peng, L.; Jia, H.; Li, H.; Bai, L.; Feng, J.; Jiang, H.; Xie, J. Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4. J. Am. Chem. Soc. 2019, 141 (14), 5640– 5644, DOI: 10.1021/jacs.9b0174667https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtVCjsLY%253D&md5=48a2071f7a7637168bf6fff2598abb63Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4Sun, Yulong; Wang, Yuechao; Liang, Xinmiao; Xia, Yuanhua; Peng, Linfeng; Jia, Huanhuan; Li, Hanxiao; Bai, Liangfei; Feng, Jiwen; Jiang, Hong; Xie, JiaJournal of the American Chemical Society (2019), 141 (14), 5640-5644CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Sodium superionic conductors are keys to develop high safety and low cost all-solid-state sodium batteries. Among developed sodium ionic conductors, antiperovskite-type ionic conductors have attracted vast interest due to their high structural tolerance and good formability. Herein, Na3OBH4 with cubic antiperovskite structure is successfully synthesized by solid-state reaction from Na2O and NaBH4. Na3OBH4 exhibits ionic cond. of 4.4 × 10-3 S cm-1 at room temp. (1.1 × 10-2 S cm-1 at 328 K) and activation energy of 0.25 eV. The ionic cond. is 4 orders of magnitude higher than the existing antiperovskite Na3OX (X = Cl, Br, I). It is shown that such enhancement is not only due to the specific cubic antiperovskite structure of Na3OBH4 but also because of the rotation of BH4 cluster anion. This work deepens the understanding of the antiperovskite structure and the role of cluster anions for superionic conduction.
- 68Zhang, Z.; Nazar, L. F. Exploiting the Paddle-Wheel Mechanism for the Design of Fast Ion Conductors. Nat. Rev. Mater. 2022, 7 (5), 389– 405, DOI: 10.1038/s41578-021-00401-0There is no corresponding record for this reference.
- 69Smith, J. G.; Siegel, D. J. Low-Temperature Paddlewheel Effect in Glassy Solid Electrolytes. Nat. Commun. 2020, 11 (1), 1483, DOI: 10.1038/s41467-020-15245-569https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlvFGjsrs%253D&md5=fb9975d74289f6b6de944f42f824c5faLow-temperature paddlewheel effect in glassy solid electrolytesSmith, Jeffrey G.; Siegel, Donald J.Nature Communications (2020), 11 (1), 1483CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic cond. remain poorly understood. Here, ab initio mol. dynamics is used to characterize migration processes in the prototype glass, 75Li2S-25P2S5. Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS43- anions. This latter effect, known as the 'paddlewheel' mechanism, is typically obsd. in high-temp. cryst. polymorphs. In contrast to the behavior of cryst. materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temp. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable cryst. analog, γ-Li3PS4, where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses contg. complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temp. Consequently, these systems may be fertile ground in the search for new solid electrolytes.
- 70Forrester, F. N.; Quirk, J. A.; Famprikis, T.; Dawson, J. A. Disentangling Cation and Anion Dynamics in Li3PS4 Solid Electrolytes. Chem. Mater. 2022, 34 (23), 10561– 10571, DOI: 10.1021/acs.chemmater.2c0263770https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVajur3E&md5=bfeb37bc4d9663d92346342208fdf759Disentangling Cation and Anion Dynamics in Li3PS4 Solid ElectrolytesForrester, Frazer N.; Quirk, James A.; Famprikis, Theodosios; Dawson, James A.Chemistry of Materials (2022), 34 (23), 10561-10571CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)A prerequisite for the realization of solid-state batteries is the development of highly conductive solid electrolytes. Li3PS4 is the archetypal member of the highly promising thiophosphate family of Li-ion conductors. Despite a multitude of investigations into this material, the underlying at.-scale features governing the roles of and the relationships between cation and anion dynamics, in its various temp.-dependent polymorphs, are yet to be fully resolved. On this basis, we provide a comprehensive mol. dynamics study to probe the fundamental mechanisms underpinning fast Li-ion diffusion in this important solid electrolyte material. We first det. the Li-ion diffusion coeffs. and corresponding activation energies in the temp.-dependent γ, β, and α polymorphs of Li3PS4 and relate them to the structural and chem. characteristics of each polymorph. The roles that both cation correlation and anion libration play in enhancing the Li-ion dynamics in Li3PS4 are then isolated and revealed. For γ- and β-Li3PS4, our simulations confirm that the interat. Li-Li interaction is pivotal in detg. (and restricting) their Li-ion diffusion. For α-Li3PS4, we quantify the significant role of Li-Li correlation and anion dynamics in dominating Li-ion transport in this polymorph for the first time. The fundamental understanding and anal. presented herein is expected to be highly applicable to other solid electrolytes where the interplay between cation and anion dynamics is crucial to enhancing ion transport.
- 71Shiiba, H.; Zettsu, N.; Yamashita, M.; Onodera, H.; Jalem, R.; Nakayama, M.; Teshima, K. Molecular Dynamics Studies on the Lithium Ion Conduction Behaviors Depending on Tilted Grain Boundaries with Various Symmetries in Garnet-Type Li7La3Zr2O12. J. Phys. Chem. C 2018, 122 (38), 21755– 21762, DOI: 10.1021/acs.jpcc.8b0627571https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsFOlt7%252FO&md5=539c0d6045737cf43e17c7a69b8bf831Molecular Dynamics Studies on the Lithium Ion Conduction Behaviors Depending on Tilted Grain Boundaries with Various Symmetries in Garnet-Type Li7La3Zr2O12Shiiba, Hiromasa; Zettsu, Nobuyuki; Yamashita, Miho; Onodera, Hitoshi; Jalem, Randy; Nakayama, Masanobu; Teshima, KatsuyaJournal of Physical Chemistry C (2018), 122 (38), 21755-21762CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Grain boundary (GB) structure is a crit. parameter that significantly affects the macroscopic properties of materials; however, the evaluation of GB characteristics by modern anal. methods remains an extremely challenging task. Li+ cond. degrdn. at the GBs of cubic Li7La3Zr2O12 (LLZO) with a garnet framework (which represents the most promising candidate material for solid electrolytes used in all-solid-state batteries) was studied by various mol. dynamics approaches combined with newly developed anal. techniques. The transboundary diffusion of Li ions was generally slower than their diffusion in the bulk regardless of the GB symmetry; however, this effect strongly depended on the concn. of Li-deficient sites (trapping Li vacancies) in the GB layer. Also, the compactness and d. of the combined GB regions represent the key parameters affecting the overall Li+ cond. of polycryst. LLZO films.
- 72Gao, B.; Jalem, R.; Tian, H.-K.; Tateyama, Y. Revealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid Electrolyte. Adv. Energy Mater. 2022, 12 (3), 2102151, DOI: 10.1002/aenm.20210215172https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXis12lu7jL&md5=a9fd48dd2f10160e7563a7ed3f08fbecRevealing Atomic-Scale Ionic Stability and Transport around Grain Boundaries of Garnet Li7La3Zr2O12 Solid ElectrolyteGao, Bo; Jalem, Randy; Tian, Hong-Kang; Tateyama, YoshitakaAdvanced Energy Materials (2022), 12 (3), 2102151CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)For real applications of all-solid-state batteries (ASSBs) to be realized, understanding and control of the grain boundaries (GBs) are essential. However, the in-depth insight into the at.-scale defect stabilities and transport of ions around GBs is still far from understood. Here, a first-principles investigation on the promising garnet Li7La3Zr2O12 (LLZO) solid electrolyte (SE) GBs is carried out. The study reveals a GB-dependent behavior for the Li-ion transport correlated to the diffusion network. Of particular note, the Σ3(112) tilt GB model exhibits a quite high Li-ion cond. comparable to that in bulk, and a fast intergranular diffusion, contrary to former discovered. Moreover, the uncovered preferential electron localization at the Σ3(112) GB leads to an increase in the electronic cond. at the GB, and the Li accumulation at the coarse GBs is revealed from the neg. Li interstitial formation energies. These factors play important roles in the dendrite formation along the GBs during Li plating in the LLZO|Li cell. These findings suggest strategies for the optimization of synthesis conditions and coating materials at the interface for preventing dendrite formation. The present comprehensive simulations provide new insights into the GB effect and engineering of the SE in ASSBs.
- 73Gao, B.; Jalem, R.; Tateyama, Y. Atomistic Insight into the Dopant Impacts at the Garnet Li7La3Zr2O12 Solid Electrolyte Grain Boundaries. J. Mater. Chem. A 2022, 10 (18), 10083– 10091, DOI: 10.1039/D2TA00545J73https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xpt1Gjsbo%253D&md5=d9d830cda74c20bd654c369fa177b156Atomistic insight into the dopant impacts at the garnet Li7La3Zr2O12 solid electrolyte grain boundariesGao, Bo; Jalem, Randy; Tateyama, YoshitakaJournal of Materials Chemistry A: Materials for Energy and Sustainability (2022), 10 (18), 10083-10091CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The garnet-type Li7La3Zr2O12 (LLZO) as one of the most promising solid electrolytes (SEs) has attracted great research attention owing to its high compatibility with Li metal anodes. Doping with a supervalent cation is an effective strategy to stabilize cubic LLZO with desired high ion cond. The behavior of dopants at the grain boundary (GB) (e.g. segregation) is expected to have a great influence on the properties of LLZO but is far from understood. Here we have performed first-principles calcns. to reveal the at.-scale impact of dopants at the GB of the LLZO SE. The results show that Al and Ga dopants at the GB are preferentially segregated at the 24d site of Li with three neighboring Li-ions, and Nb and Ta dopants prefer to locate at the 5-coordinated and partially distorted 6-coordinated Zr sites at the GB. The segregation of a Nb-like dopant at the GB will improve Li-ion cond., while the GB with an Al-like dopant shows cond. comparable to that of the undoped one and fragmentation of the Li-ion diffusion network. Moreover, the electronic state calcns. indicate electron accumulation at the doped GBs, in contrast to the mitigation effect of the dopants on dendrite formation along LLZO GBs revealed by the calcn. of Li interstitial formation energy. We also explored the potentially existing phases at the doped coarse GBs, and a series of products have been proposed. These comprehensive calcns. provide valuable atomistic insights into the dopants at the GB in the LLZO SE and substantial knowledge of optimization of this material.
- 74Cui, J.; Meng, L.; Jiang, S.; Wang, K.; Qian, J.; Wang, X. Lithium-Ion Diffusion in the Grain Boundary of Polycrystalline Solid Electrolyte Li6.75La3Zr1.5Ta0.5O12 (LLZTO): A Computer Simulation and Theoretical Study. Phys. Chem. Chem. Phys. 2022, 24 (44), 27355– 27361, DOI: 10.1039/D2CP02766F74https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVSjsLrO&md5=33baa88271e2466c714e5e1014528d6fLithium-ion diffusion in the grain boundary of polycrystalline solid electrolyte Li6.75La3Zr1.5Ta0.5O12Cui, Jiahao; Meng, Lingchen; Jiang, Shan; Wang, Kangping; Qian, Jingyu; Wang, XiyangPhysical Chemistry Chemical Physics (2022), 24 (44), 27355-27361CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Lithium-ion diffusion ability in solid electrolytes is crucial for the performance and safety of lithium-ion batteries. However, the lithium-ion diffusion coeff. of Li6.75La3Zr1.5Ta0.5O12 (LLZTO) measured exptl. is much lower than that simulated theor. because LLZTO exists widely in the polycryst. form rather than in the single-crystal form. Herein, we focus on the construction of grain boundaries in polycryst. materials to address this key issue. An amorphous structure is created by randomly throwing atoms into a virtual box, where the chem. bonds are broken and rearranged through continuous heating and annealing operations, resulting in a stable framework structure. The lithium-ion diffusion coeffs. of polycryst. LLZTO and single-crystal LLZTO calcd. via Ab initio mol. dynamics (AIMD) are consistent with the exptl. data in trend. Furthermore, the anal. of the grain boundary composed of the secondary phase in polycryst. LLZTO reveals that the continuous -O-M-O- metal oxide grid with low formation energy per atom restricts the lithium-ion migration. The lithium-ion migration barriers calcd. utilizing d. functional theory (DFT) also demonstrate the obstacle of the grain boundary from another perspective.
- 75Symington, A. R.; Molinari, M.; Dawson, J. A.; Statham, J. M.; Purton, J.; Canepa, P.; Parker, S. C. Elucidating the Nature of Grain Boundary Resistance in Lithium Lanthanum Titanate. J. Mater. Chem. A 2021, 9 (10), 6487– 6498, DOI: 10.1039/D0TA11539H75https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXjtVGjtLs%253D&md5=4512a6cce991c0533745daf969467267Elucidating the nature of grain boundary resistance in lithium lanthanum titanateSymington, Adam R.; Molinari, Marco; Dawson, James A.; Statham, Joel M.; Purton, John; Canepa, Pieremanuele; Parker, Stephen C.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (10), 6487-6498CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid electrolytes for all-solid-state batteries are generating remarkable research interest as a means to improve the safety, stability and performance of rechargeable batteries. Solid electrolytes are often polycryst. and the effect that grain boundaries have on the material properties is often not fully characterised. Here, we present a comprehensive mol. dynamics study that quantifies the effect of grain boundaries on Li-ion transport in perovskite Li3xLa(2/3)-xTiO3 (0 < x < 0.16) (LLTO). Our results predict that grain boundaries hinder Li-ion cond. by 1 to 2 orders of magnitude compared to the bulk. We attribute the poor Li-ion cond. of the grain boundaries to significant structural alterations at the grain boundaries. Our detailed anal. provides important insight into the influence of grain boundary structure on transport of Li-ions in solid electrolyte materials.
- 76Nakano, K.; Tanibata, N.; Takeda, H.; Kobayashi, R.; Nakayama, M.; Watanabe, N. Molecular Dynamics Simulation of Li-Ion Conduction at Grain Boundaries in NASICON-Type LiZr2(PO4)3 Solid Electrolytes. J. Phys. Chem. C 2021, 125 (43), 23604– 23612, DOI: 10.1021/acs.jpcc.1c0731476https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitlSjsLrO&md5=a1ecd83324695bb61dbb09286fae5a6fMolecular Dynamics Simulation of Li-Ion Conduction at Grain Boundaries in NASICON-Type LiZr2(PO4)3 Solid ElectrolytesNakano, Koki; Tanibata, Naoto; Takeda, Hayami; Kobayashi, Ryo; Nakayama, Masanobu; Watanabe, NaokiJournal of Physical Chemistry C (2021), 125 (43), 23604-23612CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Na superionic conductor-type LiZr2(PO4)3 (LZP)-related materials are considered promising solid electrolytes that can assist in realizing rechargeable all-solid-state Li-ion batteries with high Li-ion cond. and electrochem. stability. However, the grain boundary (GB) resistance considerably reduces the total Li-ion cond. of the sintered polycryst. body, which is obsd. in LZP and several other Li-ion conductive oxides. In this regard, the rational design of solid-solid interfaces is known to improve the ionic cond. Therefore, examg. the ion conduction mechanism at GBs is important from the viewpoints of practical usability and elucidation of the fundamental knowledge on dynamics in cryst. solids. In this study, 32 GB models were constructed, consisting of various Miller indexes and terminations, and the corresponding GB Li-ion conductivities were evaluated using mol. dynamics simulations with d. functional theory-derived force-field parameters. A few of the GB models exhibited improved Li-ion conductivities compared to the bulk ionic cond. Machine learning anal. using descriptors derived from interfacial structure characteristics suggested that the size of cavities around the original Li 6b sites significantly affected the GB ionic cond., which could enable the rational design of GB structures.
- 77Kobayashi, R.; Nakano, K.; Nakayama, M. Non-Equilibrium Molecular Dynamics Study on Atomistic Origin of Grain Boundary Resistivity in NASICON-Type Li-Ion Conductor. Acta Mater. 2022, 226, 117596, DOI: 10.1016/j.actamat.2021.11759677https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XmsFaksA%253D%253D&md5=bcafbf6bea38bd45c562de74626a11d3Non-equilibrium molecular dynamics study on atomistic origin of grain boundary resistivity in NASICON-type Li-ion conductorKobayashi, Ryo; Nakano, Koki; Nakayama, MasanobuActa Materialia (2022), 226 (), 117596CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)Grain boundary (GB) resistance to ion conduction in solid-state electrolytes is one of the main issues on next-generation, high-performance rechargeable batteries. Thus, it is required to understand the origin of the GB resistance from the atomistic point of view. In this paper, a method to investigate the local ion flux using the non-equil. mol. dynamics (NEMD) is proposed, and it is demonstrated that the atomistic origin of the GB resistance in NASICON-type LiZr2(PO4)3 is clarified by the local ion-flux anal. of poly-cryst. system contg. over half-million atoms in combination with Li-ion site potential energy anal. The local ion-flux anal. enables us to visualize where Li ions migrate fast or slow in poly-cryst. structures, and it is obsd., for the first time, that Li ions move toward lower reaches within grains and pass through specific regions of GBs. The Li-ion site potential energy anal. provides at.-level details of the differences between high-flux and low-flux regions. It is confirmed from the analyses that the GB resistance comes from deep Li-ion traps and high-energy Li-ion migration paths made of rings of PO4 and ZrO6 polyhedra that do not exist in the cryst. structure.
- 78Liu, Z.; Fu, W.; Payzant, E. A.; Yu, X.; Wu, Z.; Dudney, N. J.; Kiggans, J.; Hong, K.; Rondinone, A. J.; Liang, C. Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4. J. Am. Chem. Soc. 2013, 135 (3), 975– 978, DOI: 10.1021/ja311089578https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXms1Ogtg%253D%253D&md5=831a6eeeff0d028622bc5808d5afd3a5Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew; Yu, Xiang; Wu, Zili; Dudney, Nancy J.; Kiggans, Jim; Hong, Kunlun; Rondinone, Adam J.; Liang, ChengduJournal of the American Chemical Society (2013), 135 (3), 975-978CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Lithium-ion-conducting solid electrolytes hold promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic cond. and a broad electrochem. window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of the room-temp. lithium-ion cond. by 3 orders of magnitude through the creation of nanostructured Li3PS4. This material has a wide electrochem. window (5 V) and superior chem. stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance the ionic cond.: (a) the redn. of the dimensions to a nanometer-sized framework stabilizes the high-conduction β phase that occurs at elevated temps., and (b) the high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic cond. of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications, including batteries, fuel cells, sensors, photovoltaic systems, and so forth.
- 79Shen, K.; He, R.; Wang, Y.; Zhao, C.; Chen, H. Atomistic Insights into the Role of Grain Boundary in Ionic Conductivity of Polycrystalline Solid-State Electrolytes. J. Phys. Chem. C 2020, 124 (48), 26241– 26248, DOI: 10.1021/acs.jpcc.0c0732879https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitlKrs73I&md5=6433429643f724c054f047321d952361Atomistic Insights into the Role of Grain Boundary in Ionic Conductivity of Polycrystalline Solid-State ElectrolytesShen, Kun; He, Ruibin; Wang, Yixuan; Zhao, Changchun; Chen, HaoJournal of Physical Chemistry C (2020), 124 (48), 26241-26248CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)It is widely accepted that grain boundary (GB) in polycryst. solid-state electrolytes (SSEs) can substantially reduce ionic conduction, which is regarded as the most essential property for SSEs. However, the phys. origin of the GB-induced retardation effects remains unanswered. In this study, mol. dynamics simulations and first-principle calcns. were combined to reveal the role of GBs in ionic conduction via the evaluation of the thermodn.-kinetic interaction between GBs and vacancy in cubic Na3PS4. Our results suggest that the reduced ionic conduction in GBs is attributed to the segregation of Na vacancy in the GB core. The GB-blocking effects strongly depend on both vacancy segregation energy and the no. of segregation sites in the GB core, which are detd. by the GB structure. This study will shed new light on the future design of polycryst. SSEs with a high ionic cond. via grain boundary engineering.
- 80Wang, Y.; Li, G.; Shen, K.; Tian, E. The Effect of Grain Boundary on Na Ion Transport in Polycrystalline Solid-State Electrolyte Cubic Na3PS4. Mater. Res. Express 2021, 8 (2), 025508, DOI: 10.1088/2053-1591/abe7b180https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXntlals7k%253D&md5=77de402f771819d9707ed2c4a40672c5The effect of grain boundary on Na ion transport in polycrystalline solid-state electrolyte cubic Na3PS4Wang, Yixuan; Li, Gengwei; Shen, Kun; Tian, EnkeMaterials Research Express (2021), 8 (2), 025508CODEN: MREAC3; ISSN:2053-1591. (IOP Publishing Ltd.)In the polycryst. solid-state electrolytes (SSEs), ionic transport is directly linked to the properties of all solid-state batteries. Grain boundaries (GBs), as essential defects in SSE, were found to play a significant role in the overall kinetics of Na ion transport, while the mechanism is not well understood due to the complex role of GBs. In this study, the first principles and phase field calcns. are combined to explore the diffusion path and the interaction between point defects and grain boundaries in cubic Na3PS4 at different scales. The effects of point defects segregation on the overall kinetics of ionic transport were discussed in detail. By comparing the energy barriers required for ion transition along GBs and across GBs, the effect of the grain boundary on ionic diffusion can be influenced by local at. coordination. This study could help improve the fundamental understanding of ionic transport in polycryst. solid-state electrolytes, and provide guidance for designing new solid-state electrolytes with excellent ionic cond.
- 81Monroe, C.; Newman, J. The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces. J. Electrochem. Soc. 2005, 152 (2), A396, DOI: 10.1149/1.185085481https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXhs1KktLc%253D&md5=e878820c6a811396757bd7435bdb40adThe impact of elastic deformation on deposition kinetics at lithium/polymer interfacesMonroe, Charles; Newman, JohnJournal of the Electrochemical Society (2005), 152 (2), A396-A404CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Past theories of electrode stability assume that the surface tension resists the amplification of surface roughness at cathodes and show that instability at lithium/liq. interfaces cannot be prevented by surface forces alone. This work treats interfacial stability in lithium/polymer systems where the electrolyte is solid. Linear elasticity theory is employed to compute the addnl. effect of bulk mech. forces on electrode stability. The lithium and polymer are treated as Hookean elastic materials, characterized by their shear moduli and Poisson's ratios. Two-dimensional displacement distributions that satisfy force balances across a periodically deforming interface are derived; these allow computation of the stress and surface-tension forces. The incorporation of elastic effects into a kinetic model demonstrates regimes of electrolyte mech. properties where amplification of surface roughness can be inhibited. For a polymer material with Poisson's ratio similar to poly(ethylene oxide), interfacial roughening is mech. suppressed when the separator shear modulus is about twice that of lithium.
- 82Yu, S.; Siegel, D. J. Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10 (44), 38151– 38158, DOI: 10.1021/acsami.8b1722382https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFSrtrvK&md5=a4bc1fab4aac1040157f1c12c4e0c44aGrain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid ElectrolytesYu, Seungho; Siegel, Donald J.ACS Applied Materials & Interfaces (2018), 10 (44), 38151-38158CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Models based on linear elasticity suggest that a solid electrolyte with a high shear modulus will suppress dendrite formation in batteries that use metallic lithium as the neg. electrode. Nevertheless, recent expts. find that lithium can penetrate stiff solid electrolytes through microstructural features, such as grain boundaries. This failure mode emerges even in cases where the electrolyte has an av. shear modulus that is an order of magnitude larger than that of Li. Adopting the solid-electrolyte Li7La3Zr2O12 (LLZO) as a prototype, significant softening in elastic properties occurs in nanoscale regions near grain boundaries. Mol. dynamics simulations performed on tilt and twist boundaries reveal that the grain boundary shear modulus is up to 50% smaller than in bulk regions. Probably inhomogeneities in elastic properties arising from microstructural features provide a mechanism by which soft lithium can penetrate ostensibly stiff solid electrolytes.
- 83Kim, H.; Conlin, P.; Bergschneider, M.; Chung, H.; Kim, S. Y.; Cha, S. W.; Cho, M.; Cho, K. First Principles Study on Li Metallic Phase Nucleation at Grain Boundaries in a Lithium Lanthanum Titanium Oxide (LLTO) Solid Electrolyte. J. Mater. Chem. A 2023, 11 (6), 2889– 2898, DOI: 10.1039/D2TA07950J83https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhs1Siu7o%253D&md5=87dc35b963776572cb05bb17d0b2dae5First principles study on Li metallic phase nucleation at grain boundaries in a lithium lanthanum titanium oxide (LLTO) solid electrolyteKim, Hyungjun; Conlin, Patrick; Bergschneider, Matthew; Chung, Hayoung; Kim, Sung Youb; Cha, Suk Won; Cho, Maenghyo; Cho, KyeongjaeJournal of Materials Chemistry A: Materials for Energy and Sustainability (2023), 11 (6), 2889-2898CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Solid electrolytes (SEs) are crit. for next-generation all solid-state batteries with high energy d. and fire safety. However, recent studies obsd. that the Li metallic phase nucleates at the electrode interfaces as well as the interfaces between cryst. grains of SEs. Many studies have revealed the origins and control methods for Li metallic phase formation at the anode interface, but a thorough understanding of metallic Li formation at intergranular regions in SEs has not been developed yet. Through systematic DFT simulations, we present a thorough atomistic study that reveals the impact of intergranular regions on Li-metallic phase formation in SEs using the perovskite Li3xLa(2/3)-x.box.(1/3)-2xTiO3 (0 < x < 0.167) (LLTO) as a model SE. We investigated the three representative model structures for intergranular regions, which are exptl. obsd. with various microstructure configurations: (i) stoichiometric grain boundary (GB), (ii) A-site deficient GB, and (iii) intergranular pore space. In the stoichiometric GB, the GB region has an electron insulating feature regardless of A-site compns. (0 < x < 0.167). In the A-site deficient GB, however, the GB region has electronic cond., but it has a high repulsive force against Li-ions moving into the GB region. However, in the intergranular pore structure, Li-ions prefer to move with a neutral charge state into the pore space which shows a p-type conductive property. Accordingly, Li metallic phase nucleation starts in the intergranular pore space of the SE. These results elucidate the crit. role of pore space in SEs for Li metallic phase nucleation and provide an insight into the design of Li metallic phase-free SEs and further studies on SE materials.