Unveiling the Future of Li-Ion Batteries: Real-Time Insights into the Synthesis of Advanced Layered Cathode MaterialsClick to copy article linkArticle link copied!
- Dongju LeeDongju LeeDepartment of Advanced Materials Engineering, Chungbuk National University, Chungdae-ro 1, Seowon-gu, Cheongju, Chungbuk 28644, Republic of KoreaChungbuk National University Hospital, 776, 1Sunhwan-ro, Seowon-gu, Cheongju, Chungbuk 28644, Republic of KoreaMore by Dongju Lee
- Hyungsub Kim*Hyungsub Kim*[email protected]Neutron Science Division, Korea Atomic Energy Research Institute (KAERI), 111 Daedeok-daero 989 Beon-Gil, Yuseong-Gu, Daejeon 34057, Republic of KoreaMore by Hyungsub Kim
- Sang Mun Jeong*Sang Mun Jeong*[email protected]Department of Chemical Engineering, Chungbuk National University, Chungdae-ro 1, Seowon-gu, Cheongju, Chungbuk 28644, Republic of KoreaMore by Sang Mun Jeong
Abstract
Prompted by the increasing demand for high-energy Li-ion batteries (LIBs) in electric vehicles (EVs), the development of advanced layered cathode materials has attracted significant attention in recent decades. Advances in in situ and in operando characterization techniques have not only led to the successful commercialization of these materials but have also opened up new horizons in terms of the development of cathodes exhibiting enhanced energy and cycle stability. This Perspective highlights recent advances in in situ monitoring techniques during the synthesis of layered cathode materials. While previous reports have focused on the reaction mechanisms during charging/discharging, this Perspective aims to reveal the complex relationships between phase transitions and microstructural evolution during synthesis and their impacts on electrochemical performance. Furthermore, we address strategies that aid understanding of the solid-state synthesis mechanisms of layered cathode materials and offer an insightful guide for the synthesis of defect-free layered oxide cathode materials.
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Attribution (BY): Credit must be given to the creator.
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Attribution (BY): Credit must be given to the creator.
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Special Issue
Published as part of ACS Energy Letters virtual special issue “Celebrating 10 Years of the Collaborative Innovation Center of Chemistry for Energy Materials (iChEM)”.
Atomic-Scale Characterization of Layered Cathode Materials Using Diffraction Techniques
Microstructural and Morphological Characterization Using Electron Microscopy and Small-Angle Scattering Techniques
Compositional and Oxidation State Changes during Synthesis
Prospects and Outlook
Stage I (RT–500 °C) | Stage II (500–800 °C) | Stage III (Aging 4–15 h) | Stage IV (Cooling) | |
---|---|---|---|---|
Atomic Structure (XRD, neutron diffraction, PDF) | · Phase fraction (wt.%) | · c/a & I(003)/I(104) ratio | · c/a & I(003)/I(104) ratio | · Phase fraction (wt.%) of Li2Co3 or LiOH |
· Li–Ni intermixing (I(003)/I(104)) | · TM–O, Li–O bond lengths | · Li and TM Occ. in 3a, 3b sites | · c/a & I(003)/I(104) ratio | |
· TM–O, Li–O bond lengths | · Li and TM Occ. in 3a, 3b sites | · Crystallite size & Microstrain | · Li and TM Occ. in 3a, 3b sites | |
· Li occ. in LixTM2-xO2 | · Crystallite size and microstrain | · Microstrain | ||
Microstructure & morphology (SEM, TEM, SAXS, SANS) | · Micropore formation (pore size and volume) | · Crystallite growth (size) | · Crystallite growth (size) | |
· Morphology change (needle-, plate-, brick-like) | · Mesopore formation and growth (size and volume) | · Macropore formation and growth (size and volume) | · Surface reconstruction (Li–Ni reordering) | |
· Local crystal change (core–shell) | · Li–Ni ordering at particle surface | · Li–Ni ordering at particle surface | ||
Oxidation state and composition (XAS, TXM) | · Mn, Co, and Ni oxidation (Global/local TM oxidation state) | · Ni oxidation (Global/local TM oxidation state) | · Ni oxidation (Global/local TM oxidation state) | · Ni reduction |
· Local lithiation in LixTM2-xO2 | · Residual Li compounds |
Biographies
Acknowledgments
This work was supported by the National Research Foundation of Korea (NRF) and the Commercialization Promotion Agency for R&D Outcomes (COMPA) funded by the Ministry of Science and ICT (Grant No.: RS-2023-00217581, RS-2023-00304768).
References
This article references 39 other publications.
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- 12Jung, S.-K.; Kim, H.; Song, S. H.; Lee, S.; Kim, J.; Kang, K. Unveiling the Role of Transition-Metal Ions in the Thermal Degradation of Layered Ni–Co–Mn Cathodes for Lithium Rechargeable Batteries. Adv. Funct. Mater. 2022, 32, 2108790 DOI: 10.1002/adfm.202108790Google ScholarThere is no corresponding record for this reference.
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- 18Wang, F.; Bai, J. Synthesis and Processing by Design of High-Nickel Cathode Materials. Batteries Supercaps 2022, 5, e202100174 DOI: 10.1002/batt.202100174Google ScholarThere is no corresponding record for this reference.
- 19Wang, S.; Hua, W.; Missyul, A.; Darma, M. S. D.; Tayal, A.; Indris, S.; Ehrenberg, H.; Liu, L.; Knapp, M. Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich Oxides. Adv. Funct. Mater. 2021, 31, 2009949 DOI: 10.1002/adfm.202009949Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXltFyntLc%253D&md5=4dd6126b2ea5cc336b74407f84374755Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich OxidesWang, Suning; Hua, Weibo; Missyul, Alexander; Darma, Mariyam Susana Dewi; Tayal, Akhil; Indris, Sylvio; Ehrenberg, Helmut; Liu, Laijun; Knapp, MichaelAdvanced Functional Materials (2021), 31 (19), 2009949CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)Deciphering the sophisticated interplay between thermodn. and kinetics of high-temp. lithiation reaction is fundamentally significant for designing and prepg. cathode materials. Here, the formation pathway of Ni-rich layered ordered LiNi0.6Co0.2Mn0.2O2 (O-LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequil. phase transition from the reactants to a metastable disordered Li1-x(Ni0.6Co0.2Mn0.2)1+xO2 (D-LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equil. phase (O-LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D-LNCM622O is well-fitted to a model of first-order disorder-to-order transition. The long-range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady-state as a function of heating time at selected temps. The dominant kinetic pathways revealed here will be instrumental in achieving high-performance cathode materials. Importantly, the O-LNCM622O tends to form the D-LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long-range cationic (dis)ordering in the Ni-rich cathodes could affect the structural evolution during cycling and thus their electrochem. properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.
- 20Bai, J.; Sun, W.; Zhao, J.; Wang, D.; Xiao, P.; Ko, J. Y. P.; Huq, A.; Ceder, G.; Wang, F. Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides. Chem. Mater. 2020, 32, 9906– 9913, DOI: 10.1021/acs.chemmater.0c02568Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVKgsr%252FN&md5=bc72b1891816959389c2d08f3ac69121Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered OxidesBai, Jianming; Sun, Wenhao; Zhao, Jianqing; Wang, Dawei; Xiao, Penghao; Ko, Jun Young Peter; Huq, Ashfia; Ceder, Gerbrand; Wang, FengChemistry of Materials (2020), 32 (23), 9906-9913CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-nickel (Ni) systems are attractive because of their high capacity. For practical use, synthetic control of stoichiometry and structural ordering is crucial but has been nontrivial due to the complexity inherent to synthesis reactions, which often proceed via nonequil. pathways. We report here a combined in situ synchrotron X-ray diffraction and ab initio study of solid-state synthesis of layered oxides starting from acetate precursors for LiCoO2 and LiNiO2 and their solid soln. LiNi0.8Co0.2O2. While all three systems ultimately evolve into the same thermodynamically stable layered phase (R‾3m), each chem. involves distinct metastable intermediates. We explain the phase progressions using a structural template model, demonstrating that during the synthesis of LiCoO2, the formed metastable spinel polymorph (Li2Co2O4; Fd‾3m) is a kinetically facile lithiation product of spinel Co3O4-the low-temp. (LT) intermediate from the decompd. Co-acetate. Similarly, in the Ni-based systems, the acetate decompn. products, rocksalts (Ni,Co)O, topotactically template the kinetic pathways of forming disordered rocksalts (Lix(Ni,Co)2-xO2; Fm‾3m), consequently leading to off-stoichiometric Lix(Ni,Co)O2 with undesired high Li/Ni mixing. These findings highlight new opportunities for engineering precursors to form LT intermediates that template the synthesis of target phases and structural properties.
- 21Goonetilleke, D.; Suard, E.; Bergner, B.; Janek, J.; Brezesinski, T.; Bianchini, M. In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials. J. Appl. Crystallogr. 2023, 56, 1066– 1075, DOI: 10.1107/S1600576723004909Google ScholarThere is no corresponding record for this reference.
- 22Ying, B.; Fitzpatrick, J. R.; Teng, Z.; Chen, T.; Lo, T. W. B.; Siozios, V.; Murray, C. A.; Brand, H. E. A.; Day, S.; Tang, C. C.; Weatherup, R. S.; Merz, M.; Nagel, P.; Schuppler, S.; Winter, M.; Kleiner, K. Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation. Chem. Mater. 2023, 35, 1514– 1526, DOI: 10.1021/acs.chemmater.2c02639Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXitFCitrw%253D&md5=4e49a74fcdd9569f1d4515c89b43c61fMonitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron RadiationYing, Bixian; Fitzpatrick, Jack R.; Teng, Zhenjie; Chen, Tianxiang; Lo, Tsz Woon Benedict; Siozios, Vassilios; Murray, Claire A.; Brand, Helen E. A.; Day, Sarah; Tang, Chiu C.; Weatherup, Robert S.; Merz, Michael; Nagel, Peter; Schuppler, Stefan; Winter, Martin; Kleiner, KarinChemistry of Materials (2023), 35 (4), 1514-1526CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The syntheses of Ni-poor (NCM111, LiNi1/3Co1/3Mn1/3O2) and Ni-rich (NCM811 LiNi0.8Co0.1Mn0.1O2) lithium transition-metal oxides (space group R‾3m) from hydroxide precursors (Ni1/3Co1/3Mn1/3(OH)2, Ni0.8Co0.1Mn0.1(OH)2) are investigated using in situ synchrotron powder diffraction and near-edge X-ray absorption fine structure spectroscopy. The development of the layered structure of these two cathode materials proceeds via two utterly different reaction mechanisms. While the synthesis of NCM811 involves a rock salt-type intermediate phase, NCM111 reveals a layered structure throughout the entire synthesis. Moreover, the necessity and the impact of a preannealing step and a high-temp. holding step are discussed.
- 23Wu, C.; Ban, J.; Chen, T.; Wang, J.; He, Y.; Wu, Z.-g. Evolution Path of Precursor-Induced High-Temperature Lithiation Reaction during the Synthesis of Lithium-Rich Cathode Materials. ACS Omega 2024, 9, 15191– 15201, DOI: 10.1021/acsomega.3c09567Google ScholarThere is no corresponding record for this reference.
- 24Wolfman, M.; Wang, X.; Garcia, J. C.; Barai, P.; Stubbs, J. E.; Eng, P. J.; Kahvecioglu, O.; Kinnibrugh, T. L.; Madsen, K. E.; Iddir, H.; Srinivasan, V.; Fister, T. T. The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC Cathodes. Adv. Energy Mater. 2022, 12, 2102951 DOI: 10.1002/aenm.202102951Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XntFCmsrY%253D&md5=4cf50757ca4b2c6a6e7917cdea167306The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC CathodesWolfman, Mark; Wang, Xiaoping; Garcia, Juan C.; Barai, Pallab; Stubbs, Joanne E.; Eng, Peter J.; Kahvecioglu, Ozge; Kinnibrugh, Tiffany L.; Madsen, Kenneth E.; Iddir, Hakim; Srinivasan, Venkat; Fister, Tim T.Advanced Energy Materials (2022), 12 (16), 2102951CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Nanoscale morphol. has a direct impact on the performance of materials for electrochem. energy storage. Despite this importance, little is known about the evolution of primary particle morphol. nor its effect on chem. pathways during synthesis. In this study, operando characterization is combined with at.-scale and continuum simulations to clarify the relationship between morphol. of cathode primary particles and their lithiation during calcination of LiNi0.8Mn0.1Co0.1O2 (NMC-811). This combined approach reveals a key role for surface oxygen adsorption in facilitating the lithiation reaction by promoting metal diffusion and oxidn., and simultaneously providing surface sites for lithium insertion. Furthermore, oxygen surface termination is shown to increase the activation energy for sintering, leading to smaller primary particle sizes at intermediate temps. Smaller particles provide both shorter diffusion lengths for lithium incorporation and increased surface site d. for lithium insertion. These insights provide a foundation for more tailored syntheses of cathode materials with optimized performance characteristics.
- 25Jo, S.; Han, J.; Seo, S.; Kwon, O.-S.; Choi, S.; Zhang, J.; Hyun, H.; Oh, J.; Kim, J.; Chung, J.; Kim, H.; Wang, J.; Bae, J.; Moon, J.; Park, Y.-C.; Hong, M.-H.; Kim, M.; Liu, Y.; Sohn, I.; Jung, K.; Lim, J. Solid-State Reaction Heterogeneity During Calcination of Lithium-Ion Battery Cathode. Adv. Mater. 2023, 35, 2207076 DOI: 10.1002/adma.202207076Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsFyltLk%253D&md5=5af0ce591570132c60ff9fb0a13590f0Solid-State Reaction Heterogeneity During Calcination of Lithium-Ion Battery CathodeJo, Sugeun; Han, Jeongwoo; Seo, Sungjae; Kwon, Oh-Sung; Choi, Subin; Zhang, Jin; Hyun, Hyejeong; Oh, Juhyun; Kim, Juwon; Chung, Jinkyu; Kim, Hwiho; Wang, Jian; Bae, Junho; Moon, Junyeob; Park, Yoon-Cheol; Hong, Moon-Hi; Kim, Miyoung; Liu, Yijin; Sohn, Il; Jung, Keeyoung; Lim, JongwooAdvanced Materials (Weinheim, Germany) (2023), 35 (10), 2207076CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)During solid-state calcination, with increasing temp., materials undergo complex phase transitions with heterogeneous solid-state reactions and mass transport. Precise control of the calcination chem. is therefore crucial for synthesizing state-of-the-art Ni-rich layered oxides (LiNi1-x-yCoxMnyO2, NRNCM) as cathode materials for lithium-ion batteries. Although the battery performance depends on the chem. heterogeneity during NRNCM calcination, it has not yet been elucidated. Herein, through synchrotron-based X-ray, mass spectrometry microscopy, and structural analyses, it is revealed that the temp.-dependent reaction kinetics, the diffusivity of solid-state lithium sources, and the ambient oxygen control the local chem. compns. of the reaction intermediates within a calcined particle. Addnl., it is found that the variations in the reducing power of the transition metals (i.e., Ni, Co, and Mn) det. the local structures at the nanoscale. The investigation of the reaction mechanism via imaging anal. provides valuable information for tuning the calcination chem. and developing high-energy/power d. lithium-ion batteries.
- 26Kim, K. S.; Jeon, M. K.; Song, S. H.; Hong, S.; Kim, H. S.; Kim, S.-W.; Kim, J.; Oh, P.; Hwang, J.; Song, J.; Ma, J.; Woo, J.-J.; Yu, S.-H.; Kim, H. Upcycling spent cathodes into single-crystalline Ni-rich cathode materials through selective lithium extraction. J. Mater. Chem. A 2023, 11, 21222– 21230, DOI: 10.1039/D3TA03900EGoogle ScholarThere is no corresponding record for this reference.
- 27Zhao, J.; Zhang, W.; Huq, A.; Misture, S. T.; Zhang, B.; Guo, S.; Wu, L.; Zhu, Y.; Chen, Z.; Amine, K.; Pan, F.; Bai, J.; Wang, F. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes. Adv. Energy Mater. 2017, 7, 1601266 DOI: 10.1002/aenm.201601266Google ScholarThere is no corresponding record for this reference.
- 28Zhang, M.-J.; Teng, G.; Chen-Wiegart, Y.-c. K.; Duan, Y.; Ko, J. Y. P.; Zheng, J.; Thieme, J.; Dooryhee, E.; Chen, Z.; Bai, J.; Amine, K.; Pan, F.; Wang, F. Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides. J. Am. Chem. Soc. 2018, 140, 12484– 12492, DOI: 10.1021/jacs.8b06150Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1ensb7P&md5=a2949430a17dd3dec9b51948763da5b6Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered OxidesZhang, Ming-Jian; Teng, Gaofeng; Chen-Wiegart, Yu-chen Karen; Duan, Yandong; Ko, Jun Young Peter; Zheng, Jiaxin; Thieme, Juergen; Dooryhee, Eric; Chen, Zonghai; Bai, Jianming; Amine, Khalil; Pan, Feng; Wang, FengJournal of the American Chemical Society (2018), 140 (39), 12484-12492CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Metal (M) oxides are one of the most interesting and widely used solids, and many of their properties can be directly correlated to the local structural ordering within basic building units (BBUs). One particular example is the high-Ni transition metal layered oxides, potential cathode materials for Li-ion batteries whose electrochem. activity is largely detd. by the cationic ordering in octahedra (e.g., the BBUs in such systems). Yet to be firmly established is how the BBUs are inherited from precursors and subsequently evolve into the desired ordering during synthesis. Herein, a multimodal in situ X-ray characterization approach is employed to investigate the synthesis process in prepg. LiNi0.77Mn0.13Co0.10O2 from its hydroxide counterpart, at scales varying from the long-range to local individual octahedral units. Real-time observation corroborated by first-principles calcns. reveals a topotactic transformation throughout the entire process, during which the layered framework is retained; however, due to preferential oxidn. of Co and Mn over Ni, significant changes happen locally within NiO6 octahedra. Specifically, oxygen loss and the assocd. symmetry breaking occur in NiO6; as a consequence, Ni2+ ions become highly mobile and tend to mix with Li, causing high cationic disordering upon formation of the layered oxides. Only through high-temp. heat treatment, Ni is further oxidized, thereby inducing symmetry reconstruction and, concomitantly, cationic ordering within NiO6 octahedra. Findings from this study shed light on designing high-Ni layered oxide cathodes and, more broadly, various functional materials through synthetic control of the constituent BBUs.
- 29Wang, D.; Kou, R.; Ren, Y.; Sun, C.-J.; Zhao, H.; Zhang, M.-J.; Li, Y.; Huq, A.; Ko, J. Y. P.; Pan, F.; Sun, Y.-K.; Yang, Y.; Amine, K.; Bai, J.; Chen, Z.; Wang, F. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes. Adv. Mater. 2017, 29, 1606715 DOI: 10.1002/adma.201606715Google ScholarThere is no corresponding record for this reference.
- 30Wang, D.; Xin, C.; Zhang, M.; Bai, J.; Zheng, J.; Kou, R.; Peter Ko, J. Y.; Huq, A.; Zhong, G.; Sun, C.-J.; Yang, Y.; Chen, Z.; Xiao, Y.; Amine, K.; Pan, F.; Wang, F. Intrinsic Role of Cationic Substitution in Tuning Li/Ni Mixing in High-Ni Layered Oxides. Chem. Mater. 2019, 31, 2731– 2740, DOI: 10.1021/acs.chemmater.8b04673Google Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXktlOis7s%253D&md5=03550e9b9535a95a3642e7a359a11f13Intrinsic Role of Cationic Substitution in Tuning Li/Ni Mixing in High-Ni Layered OxidesWang, Dawei; Xin, Chao; Zhang, Mingjian; Bai, Jianming; Zheng, Jiaxin; Kou, Ronghui; Peter Ko, Jun Young; Huq, Ashfia; Zhong, Guiming; Sun, Cheng-Jun; Yang, Yong; Chen, Zonghai; Xiao, Yinguo; Amine, Khalil; Pan, Feng; Wang, FengChemistry of Materials (2019), 31 (8), 2731-2740CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Nickel-rich transition metal (TM) layered oxides, particularly those ones with high Ni content, attract world-wide interest for potential use as high-capacity cathodes in next-generation Li-ion batteries. However, as Ni loading increases, Li and Ni sitting at octahedra tend to mix, resulting in reduced electrochem. activity, which has been one major obstacle to their practical applications. Herein, we investigate the kinetic and thermodn. aspects of Li/Ni mixing in LiNi0.7MnxCo0.3-xO2 (0〈x〈0.3) as they are being synthesized, through a multimodal approach for quant. detn. of structural ordering and com-parison to ab initio calcns. Results from this study elucidate the role of Mn/Co substitution at Ni sites in tuning Li/Ni ordering, intrinsically through local magnetic interaction. Specifically, Co substitution facilitates Li/Ni ordering by relieving the intra-plane magnetic frustration and reducing the inter-plane super-exchange (SE) interaction; in contrast, Mn exacerbates mag-netic frustration, strengthens SE, thereby aggravating Li/Ni mixing. These findings highlight the interplay between local magnetic interactions and cationic ordering, which has yet to be fully investigated for the needs of designing high-Ni layered cathodes and, broadly, TM-based oxides for various applications.
- 31Duan, Y.; Yang, L.; Zhang, M.-J.; Chen, Z.; Bai, J.; Amine, K.; Pan, F.; Wang, F. Insights into Li/Ni ordering and surface reconstruction during synthesis of Ni-rich layered oxides. J. Mater. Chem. A 2019, 7, 513– 519, DOI: 10.1039/C8TA10553GGoogle Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVSgtbbJ&md5=370d8082e937827372a560eff35a6e71Insights into Li/Ni ordering and surface reconstruction during synthesis of Ni-rich layered oxidesDuan, Yandong; Yang, Luyi; Zhang, Ming-Jian; Chen, Zonghai; Bai, Jianming; Amine, Khalil; Pan, Feng; Wang, FengJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (2), 513-519CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Nickel-rich layered transition metal oxides (NMCs) have been intensively studied as promising cathode candidates for next-generation Li-ion batteries, known for low cost and high theor. capacity. However, the practical capacity of NMCs is largely detd. by cationic ordering and has yet to be well controlled during synthesis, largely due to the complexity and non-equil. nature of the reactions occurring in the sintering process. In this work, high-energy synchrotron X-ray diffraction is employed to investigate the kinetic and thermodn. aspects of cationic ordering during synthesis of LiNi0.7Mn0.15Co0.15O2 (NMC71515). It is found that cationic ordering in the bulk is coupled to surface reconstruction during synthesis, occurring concomitantly and both being greatly affected by Li2CO3 decompn. and Li loss at the particle surface. Through tuning the sintering temp. and time, highly ordered NMC71515 with high capacity and excellent rate capability is synthesized. The developed approach may be applied broadly to the synthesis of high-performance Ni-rich NMC and other cathode materials.
- 32Bianchini, M.; Fauth, F.; Hartmann, P.; Brezesinski, T.; Janek, J. An in situ structural study on the synthesis and decomposition of LiNiO2. J. Mater. Chem. A 2020, 8, 1808– 1820, DOI: 10.1039/C9TA12073DGoogle Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVKqsbzJ&md5=9ccba063c9e09b67b4340bf387c21f2eAn in situ structural study on the synthesis and decomposition of LiNiO2Bianchini, Matteo; Fauth, Francois; Hartmann, Pascal; Brezesinski, Torsten; Janek, JuergenJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (4), 1808-1820CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The electrification trend in the automotive industry is fueling research on pos. electrode materials with high specific capacities. The nickel content in such layered oxide systems is continuously increasing, and so is the importance of LiNiO2 (LNO). Despite decades of research, LNO still exhibits properties, closely related to its instability, that require better understanding. One of these is the difficult solid-state synthesis that never seems to yield LNO samples of perfect stoichiometry. At present, improved exptl. capabilities allow for investigating the synthesis process in unprecedented detail. Here, synchrotron X-ray diffraction is carried out in situ during calcination and decompn. of LNO at high temp., to reveal the evolution of precursor materials during solid-state synthesis. The effect is evaluated of pre-annealing the hydroxide precursors' mixt. at low temp., prior to the actual calcination at 700°. It is then shown that LNO formation is a structurally complex process, beginning from LNO seeds with a compressed rhombohedral unit cell (c/a < 4.9) within the rock salt framework. A key aspect is identified in the presence of Ni vacancies in Ni slabs, creating space for cation migration and allowing for the material's layering. The decompn. of LNO is also investigated, since it can be seen as the reverse process of synthesis. In fact, beginning already at 700°, it is in a way a byproduct of the synthesis. The change is correlated in stoichiometry with the unit cell vol. of LNO and how permanent damage is done is shown to it by even a short time at too low O2 chem. potential. Taken together, this work aims at providing insights that may be of help in optimizing the synthesis of LNO while minimizing decompn. effects. Moreover, the same information can be seen as a starting point to further studies on Ni-rich (doped) compns. of practical interest.
- 33Zhang, M.-J.; Hu, X.; Li, M.; Duan, Y.; Yang, L.; Yin, C.; Ge, M.; Xiao, X.; Lee, W.-K.; Ko, J. Y. P.; Amine, K.; Chen, Z.; Zhu, Y.; Dooryhee, E.; Bai, J.; Pan, F.; Wang, F. Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered Oxides. Adv. Energy Mater. 2019, 9, 1901915 DOI: 10.1002/aenm.201901915Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFCmtbbP&md5=458d0cc4f1e2b445089bdae7c6a86f57Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered OxidesZhang, Ming-Jian; Hu, Xiaobing; Li, Maofan; Duan, Yandong; Yang, Luyi; Yin, Chong; Ge, Mingyuan; Xiao, Xianghui; Lee, Wah-Keat; Ko, Jun Young Peter; Amine, Khalil; Chen, Zonghai; Zhu, Yimei; Dooryhee, Eric; Bai, Jianming; Pan, Feng; Wang, FengAdvanced Energy Materials (2019), 9 (43), 1901915CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNixMnyCozO2; x = 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the crit. issues of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi0.7Mn0.15Co0.15O2 with greatly enhanced rate capability is demonstrated, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface anal., is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li2CO3 accumulation, formation of a Li-deficient layer and Ni redn. at the particle surface. The reconstruction process occurs predominantly at high temps. (above 350°C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.
- 34Casas-Cabanas, M.; Palacín, M. R.; Rodríguez-Carvajal, J. Microstructural analysis of nickel hydroxide: Anisotropic size versus stacking faults. Powder Diffr. 2005, 20, 334– 344, DOI: 10.1154/1.2137340Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht12lsb%252FP&md5=b8a648ff95dcfc5e15a3660931a0075eMicrostructural analysis of nickel hydroxide. Anisotropic size versus stacking faultsCasas-Cabanas, Montse; Palacin, Maria Rosa; Rodriguez-Carvajal, JuanPowder Diffraction (2005), 20 (4), 334-344CODEN: PODIE2; ISSN:0885-7156. (American Institute of Physics)Two different approaches for studying sample's contributions to diffraction-line broadening are analyzed by applying them to several Ni hydroxide samples. Both are based in the refinement of powder diffraction data but differ in the microstructural model used. The 1st one consists in the refinement of the powder diffraction pattern using the FAULTS program, a modification of DIFFaX, which assigns peak broadening mainly to the presence of stacking faults and treats finite size effects by convolution with a Voigt function. The 2nd method makes use of the program FULLPROF, which allows the use of linear combinations of spherical harmonics to model peak broadening coming from anisotropic size effects. The complementary use of transmission electron microscopy has allowed us to evaluate the best approach for the Ni(OH)2 case. In addn., peak shifts, corresponding to reflections 10l (l≠0) were obsd. in defective Ni hydroxide samples that can be directly correlated with the degree of faulting.
- 35Gim, J.; Zhang, Y.; Gao, H.; Xu, G.-L.; Guo, F.; Ren, Y.; Amine, K.; Chen, Z. Probing solid-state reaction through microstrain: A case study on synthesis of LiCoO2. J. Power Sources 2020, 469, 228422 DOI: 10.1016/j.jpowsour.2020.228422Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFWkt7fN&md5=5bdb83819e55dc4b78aaaedf6bdb4f48Probing solid-state reaction through microstrain: A case study on synthesis of LiCoO2Gim, Jihyeon; Zhang, Yinzhi; Gao, Han; Xu, Gui-Liang; Guo, Fangmin; Ren, Yang; Amine, Khalil; Chen, ZonghaiJournal of Power Sources (2020), 469 (), 228422CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Solid-state reaction has been widely adopted as a low-cost and scalable approach to synthesize inorg. materials for industrial applications. However, a special caution must be paid to carefully control the synthesis condition in order to obtain final products with desired structure and phys./chem. properties. In this work, LiCoO2 was investigated as a model material to illustrate the complexity of the solid-state reaction, as well as its condition control. Taking the advantage of the high flux and high penetration capability of synchrotron X-ray source, in-situ high-energy X-ray diffraction was deployed to investigate the structural evolution of materials during the solid-state reaction while ex-situ high-resoln. X-ray diffraction was utilized to quantify the residual microstrains of LiCoO2. It is shown that the microstrain is a sensitive indicator to probe the completeness of the solid-state reactions, and that it also provides a more quant. way to establish the structure-property relationship of materials. It can serve as a sensitive indicator for the rational design of synthesis process for functional materials.
- 36Tang, L.; Cheng, X.; Wu, R.; Cao, T.; Lu, J.; Zhang, Y.; Zhang, Z. Monitoring the morphology evolution of LiNi0.8Mn0.1Co0.1O2 during high-temperature solid state synthesis via in situ SEM. J. Energy Chem. 2022, 66, 9– 15, DOI: 10.1016/j.jechem.2021.07.021Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFers7bF&md5=e4d332004d61680613bc4aa27b0273c2Monitoring the morphology evolution of LiNi0.8Mn0.1Co0.1O2 during high-temperature solid state synthesis via in situ SEMTang, Liang; Cheng, Xiaopeng; Wu, Rui; Cao, Tianci; Lu, Junxia; Zhang, Yuefei; Zhang, ZeJournal of Energy Chemistry (2022), 66 (), 9-15CODEN: JECOFG; ISSN:2095-4956. (Science Press)The particle morphol. detd. by the sintering process is the director factor affecting the electrochem. performance of Ni-rich NMC cathode materials. To prep. the ideal NMC particles, it is of great significance to understand the morphol. changes during sintering process. In this work, the morphol. evolution of LiNi0.8Mn0.1Co0.1O2 (NMC811) synthesis at temp. ranging from 300-1080 °C were obsd. by in situ SEM. The uniform mixt. of spherical Ni0.8Mn0.1Co0.1(OH)2 precursor and lithium sources (LiOH) was employed by high temp. solid-state process inside the SEM, which enables us to observe morphol. changes in real time. The results show that synthetic reaction of LiNi0.8Mn0.1Co0.1O2 usually includes three processes: the raw materials' dehydration, oxidn., and combination, accompanied by a significant redn. in particle size, which is important ref. to control the synthesis temp. As heating temp. rise, the morphol. of mixt. also changed from flake to brick-shaped. However, Ni nanoparticle formation is apparent at higher temp. ∼1000 °C, suggesting a structural transformation from a layered to a rock-salt-like structure. Combining the in-situ obsd. changes in size and morphol., and with the premise of ensuring the morphol. change from flakes to bricks, reducing the sintering temp. as much as possible to prevent excessive redn. in particle size and layered to a rock-salt structure transformation is recommended for prep. ideal NMC particles.
- 37Fratzl, P. Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materials. J. Appl. Crystallogr. 2003, 36, 397– 404, DOI: 10.1107/S0021889803000335Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtVOhu74%253D&md5=0c65153fd00aae575e56b3f8abd995b6Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materialsFratzl, PeterJournal of Applied Crystallography (2003), 36 (3, Pt. 1), 397-404CODEN: JACGAR; ISSN:0021-8898. (Blackwell Munksgaard)A review. Since the early days of small-angle scattering (SAS), this technique was used to characterize the structure of solid materials on the nanometer scale. Some recent developments in this field will be reviewed, focusing on alloys, ceramics and (nano-) composite materials. The large field of SAS from polymeric systems will not be covered. Classical applications of SAS are the characterization of pores or ppts. in alloys, for instance. In more recent years, a range of new applications for x-ray SAS has emerged owing to the availability of more and more brilliant (synchrotron) x-ray sources. Examples include grazing-incidence SAXS, used increasingly to characterize nano-structured surfaces on semiconductors and also on other materials. The use of a narrow x-ray beam also allows the study of extremely inhomogeneous or hierarchically structured materials by scanning SAXS. In this approach, the specimen is moved step by step across an x-ray beam with a diam. of a few micrometers (or even less), collecting a SAXS pattern at each step. In neutron SAS, the systematic use of magnetic cross sections has brought considerable progress in the study of magnetic nano-particles or nano-composites. Single cryst. or textured materials are being studied under several orientations with respect to the primary beam to yield three-dimensional (neutron or x-ray) SAS patterns. In many cases, SAS is combined with other techniques, such as electron microscopy, spectroscopy or mech. characterization, the most elegant being an in-situ combination. A no. of recent examples for the above-mentioned approaches will be given.
- 38Feng, Z.; Barai, P.; Gim, J.; Yuan, K.; Wu, Y. A.; Xie, Y.; Liu, Y.; Srinivasan, V. In Situ Monitoring of the Growth of Nickel, Manganese, and Cobalt Hydroxide Precursors during Co-Precipitation Synthesis of Li-Ion Cathode Materials. J. Electrochem. Soc. 2018, 165, A3077, DOI: 10.1149/2.0511813jesGoogle Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVOqs7bO&md5=f4e2822928095f95026be6ef9d8191dfIn situ monitoring of the growth of nickel, manganese, and cobalt hydroxide precursors during co-precipitation synthesis of Li-ion cathode materialsFeng, Zhange; Barai, Pallab; Gim, Jihyeon; Ke, Yuan; Wu, Yimin A.; Xie, Yuanyuan; Liu, Yuzi; Srinivasan, VenkatJournal of the Electrochemical Society (2018), 165 (13), A3077-A3083CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The electrochem. performance of cathode materials for Li-ion batteries depends on the morphol. of the material, which, in turn, depends on the synthesis conditions. Very few studies have focused on the impact of process conditions on the final morphol. of the cathode particles and analyzed the growth during synthesis. In this paper, the evolution of nickel, manganese, and cobalt hydroxide precursor, Ni1/3Mn1/3Co1/3(OH)2, is investigated using a combination of in situ and ex situ techniques during the commonly-used copptn. process. These include in situ wide angle X-ray scattering, in-situ ultra-small angle X-ray scattering and ex situ particle size anal. The growth rate of cryst. Ni1/3Mn1/3Co1/3(OH)2 primary particle is found to be almost const., consistent with a math. anal. of process. The growth of the Ni1/3Mn1/3Co1/3(OH)2 secondary particle and its particle size distribution revealed different growth stages for samples prepd. at different pH. These techniques are complimented with SEM and electrochem. testing to track the morphol. and performance of the hydroxide particle and the subsequent calcined LiNi1/3Mn1/3Co1/3O2 cathode active material. This study presents insights into the synthesis process and provides a deeper understanding to aid in process optimization.
- 39Lu, J.-M.; Pan, J.-Z.; Mo, Y.-M.; Fang, Q. Automated Intelligent Platforms for High-Throughput Chemical Synthesis. Artif. Intell. Chem. 2024, 2, 100057 DOI: 10.1016/j.aichem.2024.100057Google ScholarThere is no corresponding record for this reference.
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- 1Li, W.; Erickson, E. M.; Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 2020, 5, 26– 34, DOI: 10.1038/s41560-019-0513-01https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtF2itrs%253D&md5=d876f1ce2f1fbc0599dda5d99dc05436High-nickel layered oxide cathodes for lithium-based automotive batteriesLi, Wangda; Erickson, Evan M.; Manthiram, ArumugamNature Energy (2020), 5 (1), 26-34CODEN: NEANFD; ISSN:2058-7546. (Nature Research)A review. High-nickel layered oxide cathode materials will be at the forefront to enable longer driving-range elec. vehicles at more affordable costs with lithium-based batteries. A continued push to higher energy content and less usage of costly raw materials, such as cobalt, while preserving acceptable power, lifetime and safety metrics, calls for a suite of strategic compositional, morphol. and microstructural designs and efficient material prodn. processes. In this Perspective, we discuss several important design considerations for high-nickel layered oxide cathodes that will be implemented in the automotive market for the coming decade. We outline various intrinsic restraints of maximizing their energy output and compare current/emerging development roadmaps approaching low-/zero-cobalt chem. Materials prodn. is another focus, relevant to driving down costs and addressing the practical challenges of high-nickel layered oxides for demanding vehicle applications. We further assess a series of stabilization techniques on their prospects to fulfill the aggressive targets of vehicle electrification.
- 2Hong, J.; Gwon, H.; Jung, S.-K.; Ku, K.; Kang, K. Review─Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries. J. Electrochem. Soc. 2015, 162, A2447, DOI: 10.1149/2.0071514jes2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslelu73J&md5=4ba342bce36a846465371392b0e0d9c5Review-Lithium-Excess Layered Cathodes for Lithium Rechargeable BatteriesHong, Jihyun; Gwon, Hyeokjo; Jung, Sung-Kyun; Ku, Kyojin; Kang, KisukJournal of the Electrochemical Society (2015), 162 (14), A2447-A2467CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)A review. The exceptionally high gravimetric capacity of lithium-excess layered cathodes (LLCs) has generated interest in their use in lithium-ion batteries (LIBs) for high-capacity applications. Their unique electrochem. and structural properties are responsible for this high capacity, which exceeds the theor. redox capability of transition metal oxides and have been intensively investigated. However, various fundamental and practical challenges must be overcome before LLCs can be successfully commercialized. The structure of pristine LLCs, which varies with the compn. and type of transition metal species used, remains unclear. In addn., the structure continuously changes during electrochem. cycling, which further complicates its understanding. In this review, the current understanding is discussed of LLCs, including the pristine structures, redox chemistries, and structural evolution during cycling, and suggest future research directions to address the crit. issues.
- 3Wang, C.-Y.; Liu, T.; Yang, X.-G.; Ge, S.; Stanley, N. V.; Rountree, E. S.; Leng, Y.; McCarthy, B. D. Fast charging of energy-dense lithium-ion batteries. Nature 2022, 611, 485– 490, DOI: 10.1038/s41586-022-05281-03https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xis1WlsbnK&md5=3bd5261ddaede4cf0928a526e37e475cFast charging of energy-dense lithium-ion batteriesWang, Chao-Yang; Liu, Teng; Yang, Xiao-Guang; Ge, Shanhai; Stanley, Nathaniel V.; Rountree, Eric S.; Leng, Yongjun; McCarthy, Brian D.Nature (London, United Kingdom) (2022), 611 (7936), 485-490CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)Lithium-ion batteries with nickel-rich layered oxide cathodes and graphite anodes have reached specific energies of 250-300 Wh kg-1 (refs. 1,2), and it is now possible to build a 90 kWh elec. vehicle (EV) pack with a 300-mi cruise range. Unfortunately, using such massive batteries to alleviate range anxiety is ineffective for mainstream EV adoption owing to the limited raw resource supply and prohibitively high cost. Ten-minute fast charging enables downsizing of EV batteries for both affordability and sustainability, without causing range anxiety. However, fast charging of energy-dense batteries (more than 250 Wh kg-1 or higher than 4 mAh cm-2) remains a great challenge3,4. Here we combine a material-agnostic approach based on asym. temp. modulation with a thermally stable dual-salt electrolyte to achieve charging of a 265 Wh kg-1 battery to 75% (or 70%) state of charge in 12 (or 11) minutes for more than 900 (or 2,000) cycles. This is equiv. to a half million mile range in which every charge is a fast charge. Further, we build a digital twin of such a battery pack to assess its cooling and safety and demonstrate that thermally modulated 4C charging only requires air convection. This offers a compact and intrinsically safe route to cell-to-pack development. The rapid thermal modulation method to yield highly active electrochem. interfaces only during fast charging has important potential to realize both stability and fast charging of next-generation materials, including anodes like silicon and lithium metal.
- 4Sun, Y.-K. High-Capacity Layered Cathodes for Next-Generation Electric Vehicles. ACS Energy Lett. 2019, 4, 1042– 1044, DOI: 10.1021/acsenergylett.9b006524https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXoslags74%253D&md5=694453811629fb59249743266fc25bb9High-Capacity Layered Cathodes for Next-Generation Electric VehiclesSun, Yang-KookACS Energy Letters (2019), 4 (5), 1042-1044CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Boron doping substantially changed the microstructure of a conventional NCM90 cathode by generating long rod-shaped grains with a highly cryst. texture, which alleviated the internal strain that resulted from the phase transition (H2-H3) in the deeply charged state.
- 5Wu, Z.; Zeng, G.; Yin, J.; Chiang, C.-L.; Zhang, Q.; Zhang, B.; Chen, J.; Yan, Y.; Tang, Y.; Zhang, H.; Zhou, S.; Wang, Q.; Kuai, X.; Lin, Y.-G.; Gu, L.; Qiao, Y.; Sun, S.-G. Unveiling the Evolution of LiCoO2 beyond 4.6 V. ACS Energy Lett. 2023, 8, 4806– 4817, DOI: 10.1021/acsenergylett.3c01954There is no corresponding record for this reference.
- 6Sun, H. H.; Kim, U.-H.; Park, J.-H.; Park, S.-W.; Seo, D.-H.; Heller, A.; Mullins, C. B.; Yoon, C. S.; Sun, Y.-K. Transition metal-doped Ni-rich layered cathode materials for durable Li-ion batteries. Nat. Commun. 2021, 12, 6552, DOI: 10.1038/s41467-021-26815-66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisVOqtbbF&md5=6901094bb3f87e0c335fda8a91a3d439Transition metal-doped Ni-rich layered cathode materials for durable Li-ion batteriesSun, H. Hohyun; Kim, Un-Hyuck; Park, Jeong-Hyeon; Park, Sang-Wook; Seo, Dong-Hwa; Heller, Adam; Mullins, C. Buddie; Yoon, Chong S.; Sun, Yang-KookNature Communications (2021), 12 (1), 6552CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Doping is a well-known strategy to enhance the electrochem. energy storage performance of layered cathode materials. Many studies on various dopants have been reported; however, a general relationship between the dopants and their effect on the stability of the pos. electrode upon prolonged cell cycling has yet to be established. Here, we explore the impact of the oxidn. states of various dopants (i.e., Mg2+, Al3+, Ti4+, Ta5+, and Mo6+) on the electrochem., morphol., and structural properties of a Ni-rich cathode material (i.e., Li[Ni0.91Co0.09]O2). Galvanostatic cycling measurements in pouch-type Li-ion full cells show that cathodes featuring dopants with high oxidn. states significantly outperform their undoped counterparts and the dopants with low oxidn. states. In particular, Li-ion pouch cells with Ta5+- and Mo6+-doped Li[Ni0.91Co0.09]O2 cathodes retain about 81.5% of their initial specific capacity after 3000 cycles at 200 mA g-1. Furthermore, physicochem. measurements and analyses suggest substantial differences in the grain geometries and crystal lattice structures of the various cathode materials, which contribute to their widely different battery performances and correlate with the oxidn. states of their dopants.
- 7Kalluri, S.; Yoon, M.; Jo, M.; Liu, H. K.; Dou, S. X.; Cho, J.; Guo, Z. Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries. Adv. Mater. 2017, 29, 1605807 DOI: 10.1002/adma.201605807There is no corresponding record for this reference.
- 8Sun, H. H.; Ryu, H.-H.; Kim, U.-H.; Weeks, J. A.; Heller, A.; Sun, Y.-K.; Mullins, C. B. Beyond Doping and Coating: Prospective Strategies for Stable High-Capacity Layered Ni-Rich Cathodes. ACS Energy Lett. 2020, 5, 1136– 1146, DOI: 10.1021/acsenergylett.0c001918https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksVyjurw%253D&md5=f74e7ff5caccef8c882021f63b95b1a8Beyond Doping and Coating: Prospective Strategies for Stable High-Capacity Layered Ni-Rich CathodesSun, H. Hohyun; Ryu, Hoon-Hee; Kim, Un-Hyuck; Weeks, Jason A.; Heller, Adam; Sun, Yang-Kook; Mullins, C. BuddieACS Energy Letters (2020), 5 (4), 1136-1146CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. This Perspective discusses the prospective strategies for overcoming the stability and capacity trade-off assocd. with increased Ni content in layered Ni-rich Li[NixCoyMnz]O2 (NCM) and Li[NixCoyAlz]O2 (NCA) cathodes. The Ni-rich NCM and NCA cathodes have largely replaced the LiCoO2 cathodes in com. batteries because of their lower cost, higher energy d., good rate capability, and reliability that has been extensively field-tested. Nevertheless, they suffer from microcrack generation along grain boundaries and Ni3+/4+ reactivity that rapidly deteriorate electrochem. performance. Doping and coating have been efficient strategies in delaying the onset of the damage, but they fail to overcome the degrdn. There are, however, alternative strategies that directly counter the inherent degrdn. through micro- and nanostructural modifications of the Ni-rich NCM and NCA cathodes.
- 9Liu, D.; Shadike, Z.; Lin, R.; Qian, K.; Li, H.; Li, K.; Wang, S.; Yu, Q.; Liu, M.; Ganapathy, S.; Qin, X.; Yang, Q.-H.; Wagemaker, M.; Kang, F.; Yang, X.-Q.; Li, B. Review of Recent Development of In Situ/Operando Characterization Techniques for Lithium Battery Research. Adv. Mater. 2019, 31, 1806620 DOI: 10.1002/adma.201806620There is no corresponding record for this reference.
- 10Boebinger, M. G.; Lewis, J. A.; Sandoval, S. E.; McDowell, M. T. Understanding Transformations in Battery Materials Using In Situ and Operando Experiments: Progress and Outlook. ACS Energy Lett. 2020, 5, 335– 345, DOI: 10.1021/acsenergylett.9b0251410https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVygt7jF&md5=54ad09a03a037f0a9348bfb828aea5ebUnderstanding Transformations in Battery Materials Using in Situ and Operando Experiments: Progress and OutlookBoebinger, Matthew G.; Lewis, John A.; Sandoval, Stephanie E.; McDowell, Matthew T.ACS Energy Letters (2020), 5 (1), 335-345CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)A review. Over the past decade, significant progress has been made toward understanding the intricate dynamics that underlie the operation of batteries. The development of in situ and operando exptl. techniques has been crit. for revealing how materials change, transform, and degrade within battery systems during charge and discharge. This Perspective first highlights recent successes in the use of in situ and operando expts. to understand dynamics in a variety of different battery materials, including alloy/conversion electrodes, intercalation electrodes, and alkali metal anodes. We then discuss four emerging focus areas in which in situ and operando expts. are expected to make an impact. These areas include solid-state batteries, improved data analytics, the linkage of dynamics across time and length scales, and understanding the at.-scale evolution of interphases. We expect that continued progress in investigating the elaborate inner workings of battery systems across time and length scales will help to advance future battery technologies.
- 11Hong, J.; Gent, W. E.; Xiao, P.; Lim, K.; Seo, D.-H.; Wu, J.; Csernica, P. M.; Takacs, C. J.; Nordlund, D.; Sun, C.-J.; Stone, K. H.; Passarello, D.; Yang, W.; Prendergast, D.; Ceder, G.; Toney, M. F.; Chueh, W. C. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 2019, 18, 256– 265, DOI: 10.1038/s41563-018-0276-111https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmt1ygtbs%253D&md5=9713dfa3ab90c7b21046bdab7d45dd8cMetal-oxygen decoordination stabilizes anion redox in Li-rich oxidesHong, Jihyun; Gent, William E.; Xiao, Penghao; Lim, Kipil; Seo, Dong-Hwa; Wu, Jinpeng; Csernica, Peter M.; Takacs, Christopher J.; Nordlund, Dennis; Sun, Cheng-Jun; Stone, Kevin H.; Passarello, Donata; Yang, Wanli; Prendergast, David; Ceder, Gerbrand; Toney, Michael F.; Chueh, William C.Nature Materials (2019), 18 (3), 256-265CODEN: NMAACR; ISSN:1476-1122. (Nature Research)Reversible high-voltage redox chem. is an essential component of many electrochem. technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V vs. Li/Li+ in a variety of oxide materials. However, oxidn. of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidn. state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approx. 1.8 Å metal-oxygen π bonds and approx. 1.4 Å O-O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighboring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochem. properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chem.
- 12Jung, S.-K.; Kim, H.; Song, S. H.; Lee, S.; Kim, J.; Kang, K. Unveiling the Role of Transition-Metal Ions in the Thermal Degradation of Layered Ni–Co–Mn Cathodes for Lithium Rechargeable Batteries. Adv. Funct. Mater. 2022, 32, 2108790 DOI: 10.1002/adfm.202108790There is no corresponding record for this reference.
- 13Song, S. H.; Kim, H. S.; Kim, K. S.; Hong, S.; Jeon, H.; Lim, J.; Jung, Y. H.; Ahn, H.; Jang, J. D.; Kim, M.-H.; Seo, J. H.; Kwon, J.-H.; Kim, D.; Lee, Y. J.; Han, Y.-S.; Park, K.-Y.; Kim, C.; Yu, S.-H.; Park, H.; Jin, H. M.; Kim, H. Toward a Nanoscale-Defect-Free Ni-Rich Layered Oxide Cathode Through Regulated Pore Evolution for Long-Lifespan Li Rechargeable Batteries. Adv. Funct. Mater. 2024, 34, 2306654 DOI: 10.1002/adfm.202306654There is no corresponding record for this reference.
- 14Park, H.; Park, H.; Song, K.; Song, S. H.; Kang, S.; Ko, K.-H.; Eum, D.; Jeon, Y.; Kim, J.; Seong, W. M.; Kim, H.; Park, J.; Kang, K. In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathways. Nat. Chem. 2022, 14, 614– 622, DOI: 10.1038/s41557-022-00915-214https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhtVKqtb%252FM&md5=3265ee56f07f3889aee9cdcc605dbeb0In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathwaysPark, Hyeokjun; Park, Hayoung; Song, Kyung; Song, Seok Hyun; Kang, Sungsu; Ko, Kun-Hee; Eum, Donggun; Jeon, Yonggoon; Kim, Jihoon; Seong, Won Mo; Kim, Hyungsub; Park, Jungwon; Kang, KisukNature Chemistry (2022), 14 (6), 614-622CODEN: NCAHBB; ISSN:1755-4330. (Nature Portfolio)Nickel-rich layered oxides are envisaged as key near-future cathode materials for high-energy lithium-ion batteries. However, their practical application has been hindered by their inferior cycle stability, which originates from chemo-mech. failures. Here we probe the solid-state synthesis of LiNi0.6Co0.2Mn0.2O2 in real time to better understand the structural and/or morphol. changes during phase evolution. Multi-length-scale observations-using aberration-cor. transmission electron microscopy, in situ heating transmission electron microscopy and in situ X-ray diffraction-reveal that the overall synthesis is governed by the kinetic competition between the intrinsic thermal decompn. of the precursor at the core and the topotactic lithiation near the interface, which results in spatially heterogeneous intermediates. The thermal decompn. leads to the formation of intergranular voids and intragranular nanopores that are detrimental to cycling stability. Furthermore, we demonstrate that promoting topotactic lithiation during synthesis can mitigate the generation of defective structures and effectively suppress the chemo-mech. failures.
- 15Wu, Y.; Wu, H.; Deng, J.; Han, Z.; Xiao, X.; Wang, L.; Chen, Z.; Deng, Y.; He, X. Insight of Synthesis of Single Crystal Ni-Rich LiNi1–x–yCoxMnyO2 Cathodes. Adv. Energy Mater. 2024, 14, 2303758 DOI: 10.1002/aenm.202303758There is no corresponding record for this reference.
- 16Li, H.; Wang, L.; Song, Y.; Zhang, Z.; Du, A.; Tang, Y.; Wang, J.; He, X. Why the Synthesis Affects Performance of Layered Transition Metal Oxide Cathode Materials for Li-Ion Batteries. Adv. Mater. 2024, 36, 2312292 DOI: 10.1002/adma.202312292There is no corresponding record for this reference.
- 17Wang, F.; Barai, P.; Kahvecioglu, O.; Pupek, K. Z.; Bai, J.; Srinivasan, V. Process design for calcination of nickel-based cathode materials by in situ characterization and multiscale modeling. J. Mater. Res. 2022, 37, 3197– 3215, DOI: 10.1557/s43578-022-00678-zThere is no corresponding record for this reference.
- 18Wang, F.; Bai, J. Synthesis and Processing by Design of High-Nickel Cathode Materials. Batteries Supercaps 2022, 5, e202100174 DOI: 10.1002/batt.202100174There is no corresponding record for this reference.
- 19Wang, S.; Hua, W.; Missyul, A.; Darma, M. S. D.; Tayal, A.; Indris, S.; Ehrenberg, H.; Liu, L.; Knapp, M. Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich Oxides. Adv. Funct. Mater. 2021, 31, 2009949 DOI: 10.1002/adfm.20200994919https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXltFyntLc%253D&md5=4dd6126b2ea5cc336b74407f84374755Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich OxidesWang, Suning; Hua, Weibo; Missyul, Alexander; Darma, Mariyam Susana Dewi; Tayal, Akhil; Indris, Sylvio; Ehrenberg, Helmut; Liu, Laijun; Knapp, MichaelAdvanced Functional Materials (2021), 31 (19), 2009949CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)Deciphering the sophisticated interplay between thermodn. and kinetics of high-temp. lithiation reaction is fundamentally significant for designing and prepg. cathode materials. Here, the formation pathway of Ni-rich layered ordered LiNi0.6Co0.2Mn0.2O2 (O-LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequil. phase transition from the reactants to a metastable disordered Li1-x(Ni0.6Co0.2Mn0.2)1+xO2 (D-LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equil. phase (O-LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D-LNCM622O is well-fitted to a model of first-order disorder-to-order transition. The long-range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady-state as a function of heating time at selected temps. The dominant kinetic pathways revealed here will be instrumental in achieving high-performance cathode materials. Importantly, the O-LNCM622O tends to form the D-LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long-range cationic (dis)ordering in the Ni-rich cathodes could affect the structural evolution during cycling and thus their electrochem. properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.
- 20Bai, J.; Sun, W.; Zhao, J.; Wang, D.; Xiao, P.; Ko, J. Y. P.; Huq, A.; Ceder, G.; Wang, F. Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides. Chem. Mater. 2020, 32, 9906– 9913, DOI: 10.1021/acs.chemmater.0c0256820https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVKgsr%252FN&md5=bc72b1891816959389c2d08f3ac69121Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered OxidesBai, Jianming; Sun, Wenhao; Zhao, Jianqing; Wang, Dawei; Xiao, Penghao; Ko, Jun Young Peter; Huq, Ashfia; Ceder, Gerbrand; Wang, FengChemistry of Materials (2020), 32 (23), 9906-9913CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-nickel (Ni) systems are attractive because of their high capacity. For practical use, synthetic control of stoichiometry and structural ordering is crucial but has been nontrivial due to the complexity inherent to synthesis reactions, which often proceed via nonequil. pathways. We report here a combined in situ synchrotron X-ray diffraction and ab initio study of solid-state synthesis of layered oxides starting from acetate precursors for LiCoO2 and LiNiO2 and their solid soln. LiNi0.8Co0.2O2. While all three systems ultimately evolve into the same thermodynamically stable layered phase (R‾3m), each chem. involves distinct metastable intermediates. We explain the phase progressions using a structural template model, demonstrating that during the synthesis of LiCoO2, the formed metastable spinel polymorph (Li2Co2O4; Fd‾3m) is a kinetically facile lithiation product of spinel Co3O4-the low-temp. (LT) intermediate from the decompd. Co-acetate. Similarly, in the Ni-based systems, the acetate decompn. products, rocksalts (Ni,Co)O, topotactically template the kinetic pathways of forming disordered rocksalts (Lix(Ni,Co)2-xO2; Fm‾3m), consequently leading to off-stoichiometric Lix(Ni,Co)O2 with undesired high Li/Ni mixing. These findings highlight new opportunities for engineering precursors to form LT intermediates that template the synthesis of target phases and structural properties.
- 21Goonetilleke, D.; Suard, E.; Bergner, B.; Janek, J.; Brezesinski, T.; Bianchini, M. In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials. J. Appl. Crystallogr. 2023, 56, 1066– 1075, DOI: 10.1107/S1600576723004909There is no corresponding record for this reference.
- 22Ying, B.; Fitzpatrick, J. R.; Teng, Z.; Chen, T.; Lo, T. W. B.; Siozios, V.; Murray, C. A.; Brand, H. E. A.; Day, S.; Tang, C. C.; Weatherup, R. S.; Merz, M.; Nagel, P.; Schuppler, S.; Winter, M.; Kleiner, K. Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation. Chem. Mater. 2023, 35, 1514– 1526, DOI: 10.1021/acs.chemmater.2c0263922https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXitFCitrw%253D&md5=4e49a74fcdd9569f1d4515c89b43c61fMonitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron RadiationYing, Bixian; Fitzpatrick, Jack R.; Teng, Zhenjie; Chen, Tianxiang; Lo, Tsz Woon Benedict; Siozios, Vassilios; Murray, Claire A.; Brand, Helen E. A.; Day, Sarah; Tang, Chiu C.; Weatherup, Robert S.; Merz, Michael; Nagel, Peter; Schuppler, Stefan; Winter, Martin; Kleiner, KarinChemistry of Materials (2023), 35 (4), 1514-1526CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)The syntheses of Ni-poor (NCM111, LiNi1/3Co1/3Mn1/3O2) and Ni-rich (NCM811 LiNi0.8Co0.1Mn0.1O2) lithium transition-metal oxides (space group R‾3m) from hydroxide precursors (Ni1/3Co1/3Mn1/3(OH)2, Ni0.8Co0.1Mn0.1(OH)2) are investigated using in situ synchrotron powder diffraction and near-edge X-ray absorption fine structure spectroscopy. The development of the layered structure of these two cathode materials proceeds via two utterly different reaction mechanisms. While the synthesis of NCM811 involves a rock salt-type intermediate phase, NCM111 reveals a layered structure throughout the entire synthesis. Moreover, the necessity and the impact of a preannealing step and a high-temp. holding step are discussed.
- 23Wu, C.; Ban, J.; Chen, T.; Wang, J.; He, Y.; Wu, Z.-g. Evolution Path of Precursor-Induced High-Temperature Lithiation Reaction during the Synthesis of Lithium-Rich Cathode Materials. ACS Omega 2024, 9, 15191– 15201, DOI: 10.1021/acsomega.3c09567There is no corresponding record for this reference.
- 24Wolfman, M.; Wang, X.; Garcia, J. C.; Barai, P.; Stubbs, J. E.; Eng, P. J.; Kahvecioglu, O.; Kinnibrugh, T. L.; Madsen, K. E.; Iddir, H.; Srinivasan, V.; Fister, T. T. The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC Cathodes. Adv. Energy Mater. 2022, 12, 2102951 DOI: 10.1002/aenm.20210295124https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XntFCmsrY%253D&md5=4cf50757ca4b2c6a6e7917cdea167306The Importance of Surface Oxygen for Lithiation and Morphology Evolution during Calcination of High-Nickel NMC CathodesWolfman, Mark; Wang, Xiaoping; Garcia, Juan C.; Barai, Pallab; Stubbs, Joanne E.; Eng, Peter J.; Kahvecioglu, Ozge; Kinnibrugh, Tiffany L.; Madsen, Kenneth E.; Iddir, Hakim; Srinivasan, Venkat; Fister, Tim T.Advanced Energy Materials (2022), 12 (16), 2102951CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Nanoscale morphol. has a direct impact on the performance of materials for electrochem. energy storage. Despite this importance, little is known about the evolution of primary particle morphol. nor its effect on chem. pathways during synthesis. In this study, operando characterization is combined with at.-scale and continuum simulations to clarify the relationship between morphol. of cathode primary particles and their lithiation during calcination of LiNi0.8Mn0.1Co0.1O2 (NMC-811). This combined approach reveals a key role for surface oxygen adsorption in facilitating the lithiation reaction by promoting metal diffusion and oxidn., and simultaneously providing surface sites for lithium insertion. Furthermore, oxygen surface termination is shown to increase the activation energy for sintering, leading to smaller primary particle sizes at intermediate temps. Smaller particles provide both shorter diffusion lengths for lithium incorporation and increased surface site d. for lithium insertion. These insights provide a foundation for more tailored syntheses of cathode materials with optimized performance characteristics.
- 25Jo, S.; Han, J.; Seo, S.; Kwon, O.-S.; Choi, S.; Zhang, J.; Hyun, H.; Oh, J.; Kim, J.; Chung, J.; Kim, H.; Wang, J.; Bae, J.; Moon, J.; Park, Y.-C.; Hong, M.-H.; Kim, M.; Liu, Y.; Sohn, I.; Jung, K.; Lim, J. Solid-State Reaction Heterogeneity During Calcination of Lithium-Ion Battery Cathode. Adv. Mater. 2023, 35, 2207076 DOI: 10.1002/adma.20220707625https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXhsFyltLk%253D&md5=5af0ce591570132c60ff9fb0a13590f0Solid-State Reaction Heterogeneity During Calcination of Lithium-Ion Battery CathodeJo, Sugeun; Han, Jeongwoo; Seo, Sungjae; Kwon, Oh-Sung; Choi, Subin; Zhang, Jin; Hyun, Hyejeong; Oh, Juhyun; Kim, Juwon; Chung, Jinkyu; Kim, Hwiho; Wang, Jian; Bae, Junho; Moon, Junyeob; Park, Yoon-Cheol; Hong, Moon-Hi; Kim, Miyoung; Liu, Yijin; Sohn, Il; Jung, Keeyoung; Lim, JongwooAdvanced Materials (Weinheim, Germany) (2023), 35 (10), 2207076CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)During solid-state calcination, with increasing temp., materials undergo complex phase transitions with heterogeneous solid-state reactions and mass transport. Precise control of the calcination chem. is therefore crucial for synthesizing state-of-the-art Ni-rich layered oxides (LiNi1-x-yCoxMnyO2, NRNCM) as cathode materials for lithium-ion batteries. Although the battery performance depends on the chem. heterogeneity during NRNCM calcination, it has not yet been elucidated. Herein, through synchrotron-based X-ray, mass spectrometry microscopy, and structural analyses, it is revealed that the temp.-dependent reaction kinetics, the diffusivity of solid-state lithium sources, and the ambient oxygen control the local chem. compns. of the reaction intermediates within a calcined particle. Addnl., it is found that the variations in the reducing power of the transition metals (i.e., Ni, Co, and Mn) det. the local structures at the nanoscale. The investigation of the reaction mechanism via imaging anal. provides valuable information for tuning the calcination chem. and developing high-energy/power d. lithium-ion batteries.
- 26Kim, K. S.; Jeon, M. K.; Song, S. H.; Hong, S.; Kim, H. S.; Kim, S.-W.; Kim, J.; Oh, P.; Hwang, J.; Song, J.; Ma, J.; Woo, J.-J.; Yu, S.-H.; Kim, H. Upcycling spent cathodes into single-crystalline Ni-rich cathode materials through selective lithium extraction. J. Mater. Chem. A 2023, 11, 21222– 21230, DOI: 10.1039/D3TA03900EThere is no corresponding record for this reference.
- 27Zhao, J.; Zhang, W.; Huq, A.; Misture, S. T.; Zhang, B.; Guo, S.; Wu, L.; Zhu, Y.; Chen, Z.; Amine, K.; Pan, F.; Bai, J.; Wang, F. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes. Adv. Energy Mater. 2017, 7, 1601266 DOI: 10.1002/aenm.201601266There is no corresponding record for this reference.
- 28Zhang, M.-J.; Teng, G.; Chen-Wiegart, Y.-c. K.; Duan, Y.; Ko, J. Y. P.; Zheng, J.; Thieme, J.; Dooryhee, E.; Chen, Z.; Bai, J.; Amine, K.; Pan, F.; Wang, F. Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered Oxides. J. Am. Chem. Soc. 2018, 140, 12484– 12492, DOI: 10.1021/jacs.8b0615028https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1ensb7P&md5=a2949430a17dd3dec9b51948763da5b6Cationic Ordering Coupled to Reconstruction of Basic Building Units during Synthesis of High-Ni Layered OxidesZhang, Ming-Jian; Teng, Gaofeng; Chen-Wiegart, Yu-chen Karen; Duan, Yandong; Ko, Jun Young Peter; Zheng, Jiaxin; Thieme, Juergen; Dooryhee, Eric; Chen, Zonghai; Bai, Jianming; Amine, Khalil; Pan, Feng; Wang, FengJournal of the American Chemical Society (2018), 140 (39), 12484-12492CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Metal (M) oxides are one of the most interesting and widely used solids, and many of their properties can be directly correlated to the local structural ordering within basic building units (BBUs). One particular example is the high-Ni transition metal layered oxides, potential cathode materials for Li-ion batteries whose electrochem. activity is largely detd. by the cationic ordering in octahedra (e.g., the BBUs in such systems). Yet to be firmly established is how the BBUs are inherited from precursors and subsequently evolve into the desired ordering during synthesis. Herein, a multimodal in situ X-ray characterization approach is employed to investigate the synthesis process in prepg. LiNi0.77Mn0.13Co0.10O2 from its hydroxide counterpart, at scales varying from the long-range to local individual octahedral units. Real-time observation corroborated by first-principles calcns. reveals a topotactic transformation throughout the entire process, during which the layered framework is retained; however, due to preferential oxidn. of Co and Mn over Ni, significant changes happen locally within NiO6 octahedra. Specifically, oxygen loss and the assocd. symmetry breaking occur in NiO6; as a consequence, Ni2+ ions become highly mobile and tend to mix with Li, causing high cationic disordering upon formation of the layered oxides. Only through high-temp. heat treatment, Ni is further oxidized, thereby inducing symmetry reconstruction and, concomitantly, cationic ordering within NiO6 octahedra. Findings from this study shed light on designing high-Ni layered oxide cathodes and, more broadly, various functional materials through synthetic control of the constituent BBUs.
- 29Wang, D.; Kou, R.; Ren, Y.; Sun, C.-J.; Zhao, H.; Zhang, M.-J.; Li, Y.; Huq, A.; Ko, J. Y. P.; Pan, F.; Sun, Y.-K.; Yang, Y.; Amine, K.; Bai, J.; Chen, Z.; Wang, F. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes. Adv. Mater. 2017, 29, 1606715 DOI: 10.1002/adma.201606715There is no corresponding record for this reference.
- 30Wang, D.; Xin, C.; Zhang, M.; Bai, J.; Zheng, J.; Kou, R.; Peter Ko, J. Y.; Huq, A.; Zhong, G.; Sun, C.-J.; Yang, Y.; Chen, Z.; Xiao, Y.; Amine, K.; Pan, F.; Wang, F. Intrinsic Role of Cationic Substitution in Tuning Li/Ni Mixing in High-Ni Layered Oxides. Chem. Mater. 2019, 31, 2731– 2740, DOI: 10.1021/acs.chemmater.8b0467330https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXktlOis7s%253D&md5=03550e9b9535a95a3642e7a359a11f13Intrinsic Role of Cationic Substitution in Tuning Li/Ni Mixing in High-Ni Layered OxidesWang, Dawei; Xin, Chao; Zhang, Mingjian; Bai, Jianming; Zheng, Jiaxin; Kou, Ronghui; Peter Ko, Jun Young; Huq, Ashfia; Zhong, Guiming; Sun, Cheng-Jun; Yang, Yong; Chen, Zonghai; Xiao, Yinguo; Amine, Khalil; Pan, Feng; Wang, FengChemistry of Materials (2019), 31 (8), 2731-2740CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Nickel-rich transition metal (TM) layered oxides, particularly those ones with high Ni content, attract world-wide interest for potential use as high-capacity cathodes in next-generation Li-ion batteries. However, as Ni loading increases, Li and Ni sitting at octahedra tend to mix, resulting in reduced electrochem. activity, which has been one major obstacle to their practical applications. Herein, we investigate the kinetic and thermodn. aspects of Li/Ni mixing in LiNi0.7MnxCo0.3-xO2 (0〈x〈0.3) as they are being synthesized, through a multimodal approach for quant. detn. of structural ordering and com-parison to ab initio calcns. Results from this study elucidate the role of Mn/Co substitution at Ni sites in tuning Li/Ni ordering, intrinsically through local magnetic interaction. Specifically, Co substitution facilitates Li/Ni ordering by relieving the intra-plane magnetic frustration and reducing the inter-plane super-exchange (SE) interaction; in contrast, Mn exacerbates mag-netic frustration, strengthens SE, thereby aggravating Li/Ni mixing. These findings highlight the interplay between local magnetic interactions and cationic ordering, which has yet to be fully investigated for the needs of designing high-Ni layered cathodes and, broadly, TM-based oxides for various applications.
- 31Duan, Y.; Yang, L.; Zhang, M.-J.; Chen, Z.; Bai, J.; Amine, K.; Pan, F.; Wang, F. Insights into Li/Ni ordering and surface reconstruction during synthesis of Ni-rich layered oxides. J. Mater. Chem. A 2019, 7, 513– 519, DOI: 10.1039/C8TA10553G31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVSgtbbJ&md5=370d8082e937827372a560eff35a6e71Insights into Li/Ni ordering and surface reconstruction during synthesis of Ni-rich layered oxidesDuan, Yandong; Yang, Luyi; Zhang, Ming-Jian; Chen, Zonghai; Bai, Jianming; Amine, Khalil; Pan, Feng; Wang, FengJournal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (2), 513-519CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Nickel-rich layered transition metal oxides (NMCs) have been intensively studied as promising cathode candidates for next-generation Li-ion batteries, known for low cost and high theor. capacity. However, the practical capacity of NMCs is largely detd. by cationic ordering and has yet to be well controlled during synthesis, largely due to the complexity and non-equil. nature of the reactions occurring in the sintering process. In this work, high-energy synchrotron X-ray diffraction is employed to investigate the kinetic and thermodn. aspects of cationic ordering during synthesis of LiNi0.7Mn0.15Co0.15O2 (NMC71515). It is found that cationic ordering in the bulk is coupled to surface reconstruction during synthesis, occurring concomitantly and both being greatly affected by Li2CO3 decompn. and Li loss at the particle surface. Through tuning the sintering temp. and time, highly ordered NMC71515 with high capacity and excellent rate capability is synthesized. The developed approach may be applied broadly to the synthesis of high-performance Ni-rich NMC and other cathode materials.
- 32Bianchini, M.; Fauth, F.; Hartmann, P.; Brezesinski, T.; Janek, J. An in situ structural study on the synthesis and decomposition of LiNiO2. J. Mater. Chem. A 2020, 8, 1808– 1820, DOI: 10.1039/C9TA12073D32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVKqsbzJ&md5=9ccba063c9e09b67b4340bf387c21f2eAn in situ structural study on the synthesis and decomposition of LiNiO2Bianchini, Matteo; Fauth, Francois; Hartmann, Pascal; Brezesinski, Torsten; Janek, JuergenJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (4), 1808-1820CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The electrification trend in the automotive industry is fueling research on pos. electrode materials with high specific capacities. The nickel content in such layered oxide systems is continuously increasing, and so is the importance of LiNiO2 (LNO). Despite decades of research, LNO still exhibits properties, closely related to its instability, that require better understanding. One of these is the difficult solid-state synthesis that never seems to yield LNO samples of perfect stoichiometry. At present, improved exptl. capabilities allow for investigating the synthesis process in unprecedented detail. Here, synchrotron X-ray diffraction is carried out in situ during calcination and decompn. of LNO at high temp., to reveal the evolution of precursor materials during solid-state synthesis. The effect is evaluated of pre-annealing the hydroxide precursors' mixt. at low temp., prior to the actual calcination at 700°. It is then shown that LNO formation is a structurally complex process, beginning from LNO seeds with a compressed rhombohedral unit cell (c/a < 4.9) within the rock salt framework. A key aspect is identified in the presence of Ni vacancies in Ni slabs, creating space for cation migration and allowing for the material's layering. The decompn. of LNO is also investigated, since it can be seen as the reverse process of synthesis. In fact, beginning already at 700°, it is in a way a byproduct of the synthesis. The change is correlated in stoichiometry with the unit cell vol. of LNO and how permanent damage is done is shown to it by even a short time at too low O2 chem. potential. Taken together, this work aims at providing insights that may be of help in optimizing the synthesis of LNO while minimizing decompn. effects. Moreover, the same information can be seen as a starting point to further studies on Ni-rich (doped) compns. of practical interest.
- 33Zhang, M.-J.; Hu, X.; Li, M.; Duan, Y.; Yang, L.; Yin, C.; Ge, M.; Xiao, X.; Lee, W.-K.; Ko, J. Y. P.; Amine, K.; Chen, Z.; Zhu, Y.; Dooryhee, E.; Bai, J.; Pan, F.; Wang, F. Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered Oxides. Adv. Energy Mater. 2019, 9, 1901915 DOI: 10.1002/aenm.20190191533https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFCmtbbP&md5=458d0cc4f1e2b445089bdae7c6a86f57Cooling Induced Surface Reconstruction during Synthesis of High-Ni Layered OxidesZhang, Ming-Jian; Hu, Xiaobing; Li, Maofan; Duan, Yandong; Yang, Luyi; Yin, Chong; Ge, Mingyuan; Xiao, Xianghui; Lee, Wah-Keat; Ko, Jun Young Peter; Amine, Khalil; Chen, Zonghai; Zhu, Yimei; Dooryhee, Eric; Bai, Jianming; Pan, Feng; Wang, FengAdvanced Energy Materials (2019), 9 (43), 1901915CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)Transition metal layered oxides have been the dominant cathodes in lithium-ion batteries, and among them, high-Ni ones (LiNixMnyCozO2; x = 0.7) with greatly boosted capacity and reduced cost are of particular interest for large-scale applications. The high Ni loading, on the other hand, raises the crit. issues of surface instability and poor rate performance. The rational design of synthesis leading to layered LiNi0.7Mn0.15Co0.15O2 with greatly enhanced rate capability is demonstrated, by implementing a quenching process alternative to the general slow cooling. In situ synchrotron X-ray diffraction, coupled with surface anal., is applied to studies of the synthesis process, revealing cooling-induced surface reconstruction involving Li2CO3 accumulation, formation of a Li-deficient layer and Ni redn. at the particle surface. The reconstruction process occurs predominantly at high temps. (above 350°C) and is highly cooling-rate dependent, implying that surface reconstruction can be suppressed through synthetic control, i.e., quenching to improve the surface stability and rate performance of the synthesized materials. These findings may provide guidance to rational synthesis of high-Ni cathode materials.
- 34Casas-Cabanas, M.; Palacín, M. R.; Rodríguez-Carvajal, J. Microstructural analysis of nickel hydroxide: Anisotropic size versus stacking faults. Powder Diffr. 2005, 20, 334– 344, DOI: 10.1154/1.213734034https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXht12lsb%252FP&md5=b8a648ff95dcfc5e15a3660931a0075eMicrostructural analysis of nickel hydroxide. Anisotropic size versus stacking faultsCasas-Cabanas, Montse; Palacin, Maria Rosa; Rodriguez-Carvajal, JuanPowder Diffraction (2005), 20 (4), 334-344CODEN: PODIE2; ISSN:0885-7156. (American Institute of Physics)Two different approaches for studying sample's contributions to diffraction-line broadening are analyzed by applying them to several Ni hydroxide samples. Both are based in the refinement of powder diffraction data but differ in the microstructural model used. The 1st one consists in the refinement of the powder diffraction pattern using the FAULTS program, a modification of DIFFaX, which assigns peak broadening mainly to the presence of stacking faults and treats finite size effects by convolution with a Voigt function. The 2nd method makes use of the program FULLPROF, which allows the use of linear combinations of spherical harmonics to model peak broadening coming from anisotropic size effects. The complementary use of transmission electron microscopy has allowed us to evaluate the best approach for the Ni(OH)2 case. In addn., peak shifts, corresponding to reflections 10l (l≠0) were obsd. in defective Ni hydroxide samples that can be directly correlated with the degree of faulting.
- 35Gim, J.; Zhang, Y.; Gao, H.; Xu, G.-L.; Guo, F.; Ren, Y.; Amine, K.; Chen, Z. Probing solid-state reaction through microstrain: A case study on synthesis of LiCoO2. J. Power Sources 2020, 469, 228422 DOI: 10.1016/j.jpowsour.2020.22842235https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFWkt7fN&md5=5bdb83819e55dc4b78aaaedf6bdb4f48Probing solid-state reaction through microstrain: A case study on synthesis of LiCoO2Gim, Jihyeon; Zhang, Yinzhi; Gao, Han; Xu, Gui-Liang; Guo, Fangmin; Ren, Yang; Amine, Khalil; Chen, ZonghaiJournal of Power Sources (2020), 469 (), 228422CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Solid-state reaction has been widely adopted as a low-cost and scalable approach to synthesize inorg. materials for industrial applications. However, a special caution must be paid to carefully control the synthesis condition in order to obtain final products with desired structure and phys./chem. properties. In this work, LiCoO2 was investigated as a model material to illustrate the complexity of the solid-state reaction, as well as its condition control. Taking the advantage of the high flux and high penetration capability of synchrotron X-ray source, in-situ high-energy X-ray diffraction was deployed to investigate the structural evolution of materials during the solid-state reaction while ex-situ high-resoln. X-ray diffraction was utilized to quantify the residual microstrains of LiCoO2. It is shown that the microstrain is a sensitive indicator to probe the completeness of the solid-state reactions, and that it also provides a more quant. way to establish the structure-property relationship of materials. It can serve as a sensitive indicator for the rational design of synthesis process for functional materials.
- 36Tang, L.; Cheng, X.; Wu, R.; Cao, T.; Lu, J.; Zhang, Y.; Zhang, Z. Monitoring the morphology evolution of LiNi0.8Mn0.1Co0.1O2 during high-temperature solid state synthesis via in situ SEM. J. Energy Chem. 2022, 66, 9– 15, DOI: 10.1016/j.jechem.2021.07.02136https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFers7bF&md5=e4d332004d61680613bc4aa27b0273c2Monitoring the morphology evolution of LiNi0.8Mn0.1Co0.1O2 during high-temperature solid state synthesis via in situ SEMTang, Liang; Cheng, Xiaopeng; Wu, Rui; Cao, Tianci; Lu, Junxia; Zhang, Yuefei; Zhang, ZeJournal of Energy Chemistry (2022), 66 (), 9-15CODEN: JECOFG; ISSN:2095-4956. (Science Press)The particle morphol. detd. by the sintering process is the director factor affecting the electrochem. performance of Ni-rich NMC cathode materials. To prep. the ideal NMC particles, it is of great significance to understand the morphol. changes during sintering process. In this work, the morphol. evolution of LiNi0.8Mn0.1Co0.1O2 (NMC811) synthesis at temp. ranging from 300-1080 °C were obsd. by in situ SEM. The uniform mixt. of spherical Ni0.8Mn0.1Co0.1(OH)2 precursor and lithium sources (LiOH) was employed by high temp. solid-state process inside the SEM, which enables us to observe morphol. changes in real time. The results show that synthetic reaction of LiNi0.8Mn0.1Co0.1O2 usually includes three processes: the raw materials' dehydration, oxidn., and combination, accompanied by a significant redn. in particle size, which is important ref. to control the synthesis temp. As heating temp. rise, the morphol. of mixt. also changed from flake to brick-shaped. However, Ni nanoparticle formation is apparent at higher temp. ∼1000 °C, suggesting a structural transformation from a layered to a rock-salt-like structure. Combining the in-situ obsd. changes in size and morphol., and with the premise of ensuring the morphol. change from flakes to bricks, reducing the sintering temp. as much as possible to prevent excessive redn. in particle size and layered to a rock-salt structure transformation is recommended for prep. ideal NMC particles.
- 37Fratzl, P. Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materials. J. Appl. Crystallogr. 2003, 36, 397– 404, DOI: 10.1107/S002188980300033537https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtVOhu74%253D&md5=0c65153fd00aae575e56b3f8abd995b6Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materialsFratzl, PeterJournal of Applied Crystallography (2003), 36 (3, Pt. 1), 397-404CODEN: JACGAR; ISSN:0021-8898. (Blackwell Munksgaard)A review. Since the early days of small-angle scattering (SAS), this technique was used to characterize the structure of solid materials on the nanometer scale. Some recent developments in this field will be reviewed, focusing on alloys, ceramics and (nano-) composite materials. The large field of SAS from polymeric systems will not be covered. Classical applications of SAS are the characterization of pores or ppts. in alloys, for instance. In more recent years, a range of new applications for x-ray SAS has emerged owing to the availability of more and more brilliant (synchrotron) x-ray sources. Examples include grazing-incidence SAXS, used increasingly to characterize nano-structured surfaces on semiconductors and also on other materials. The use of a narrow x-ray beam also allows the study of extremely inhomogeneous or hierarchically structured materials by scanning SAXS. In this approach, the specimen is moved step by step across an x-ray beam with a diam. of a few micrometers (or even less), collecting a SAXS pattern at each step. In neutron SAS, the systematic use of magnetic cross sections has brought considerable progress in the study of magnetic nano-particles or nano-composites. Single cryst. or textured materials are being studied under several orientations with respect to the primary beam to yield three-dimensional (neutron or x-ray) SAS patterns. In many cases, SAS is combined with other techniques, such as electron microscopy, spectroscopy or mech. characterization, the most elegant being an in-situ combination. A no. of recent examples for the above-mentioned approaches will be given.
- 38Feng, Z.; Barai, P.; Gim, J.; Yuan, K.; Wu, Y. A.; Xie, Y.; Liu, Y.; Srinivasan, V. In Situ Monitoring of the Growth of Nickel, Manganese, and Cobalt Hydroxide Precursors during Co-Precipitation Synthesis of Li-Ion Cathode Materials. J. Electrochem. Soc. 2018, 165, A3077, DOI: 10.1149/2.0511813jes38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVOqs7bO&md5=f4e2822928095f95026be6ef9d8191dfIn situ monitoring of the growth of nickel, manganese, and cobalt hydroxide precursors during co-precipitation synthesis of Li-ion cathode materialsFeng, Zhange; Barai, Pallab; Gim, Jihyeon; Ke, Yuan; Wu, Yimin A.; Xie, Yuanyuan; Liu, Yuzi; Srinivasan, VenkatJournal of the Electrochemical Society (2018), 165 (13), A3077-A3083CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The electrochem. performance of cathode materials for Li-ion batteries depends on the morphol. of the material, which, in turn, depends on the synthesis conditions. Very few studies have focused on the impact of process conditions on the final morphol. of the cathode particles and analyzed the growth during synthesis. In this paper, the evolution of nickel, manganese, and cobalt hydroxide precursor, Ni1/3Mn1/3Co1/3(OH)2, is investigated using a combination of in situ and ex situ techniques during the commonly-used copptn. process. These include in situ wide angle X-ray scattering, in-situ ultra-small angle X-ray scattering and ex situ particle size anal. The growth rate of cryst. Ni1/3Mn1/3Co1/3(OH)2 primary particle is found to be almost const., consistent with a math. anal. of process. The growth of the Ni1/3Mn1/3Co1/3(OH)2 secondary particle and its particle size distribution revealed different growth stages for samples prepd. at different pH. These techniques are complimented with SEM and electrochem. testing to track the morphol. and performance of the hydroxide particle and the subsequent calcined LiNi1/3Mn1/3Co1/3O2 cathode active material. This study presents insights into the synthesis process and provides a deeper understanding to aid in process optimization.
- 39Lu, J.-M.; Pan, J.-Z.; Mo, Y.-M.; Fang, Q. Automated Intelligent Platforms for High-Throughput Chemical Synthesis. Artif. Intell. Chem. 2024, 2, 100057 DOI: 10.1016/j.aichem.2024.100057There is no corresponding record for this reference.