Species Distribution During Solid Electrolyte Interphase Formation on Lithium Using MD/DFT-Parameterized Kinetic Monte Carlo SimulationsClick to copy article linkArticle link copied!
- Michail GerasimovMichail GerasimovInstitute for Applied Materials − Electrochemical Technologies, Karlsruhe Institute of Technology, Karlsruhe 76131, GermanyMore by Michail Gerasimov
- Fernando A. SotoFernando A. SotoPenn State Greater Allegheny, McKeesport, Pennsylvania 15132, United StatesMore by Fernando A. Soto
- Janika WagnerJanika WagnerInstitute for Applied Materials − Electrochemical Technologies, Karlsruhe Institute of Technology, Karlsruhe 76131, GermanyMore by Janika Wagner
- Florian BaakesFlorian BaakesInstitute for Applied Materials − Electrochemical Technologies, Karlsruhe Institute of Technology, Karlsruhe 76131, GermanyMore by Florian Baakes
- Ningxuan GuoNingxuan GuoMcCloskey Laboratory, University of California, Berkeley, California 94720, United StatesMore by Ningxuan Guo
- Francisco Ospina-AcevedoFrancisco Ospina-AcevedoDepartment of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United StatesMore by Francisco Ospina-Acevedo
- Fridolin RöderFridolin RöderBavarian Center for Battery Technology (BayBatt), University of Bayreuth, 95448 Bayreuth, GermanyMore by Fridolin Röder
- Perla B. Balbuena*Perla B. Balbuena*E-mail: [email protected]Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United StatesMore by Perla B. Balbuena
- Ulrike Krewer*Ulrike Krewer*E-mail: [email protected]Institute for Applied Materials − Electrochemical Technologies, Karlsruhe Institute of Technology, Karlsruhe 76131, GermanyMore by Ulrike Krewer
Abstract
Lithium metal batteries are one of the promising technologies for future energy storage. One open challenge is the generation of a stable and well performing Solid Electrolyte Interphase (SEI) between lithium metal and electrolyte. Understanding the complex interaction of reactions at the lithium surface and the resulting SEI is crucial for knowledge-driven improvement of the SEI. This study reveals the internal species distribution and geometrical aspects of the native SEI during formation by model-based analysis. To achieve this, a combination of molecular dynamics, density functional theory, and stand-alone 3D-kinetic Monte Carlo simulations is used. The kinetic Monte Carlo model determines the SEI growth features over a long time and length scale so that the SEI can be analyzed quantitatively. The simulation confirms the frequently postulated layered SEI structure arising from the decomposition of an ethylene carbonate/lithium hexafluorophosphate (2 M) electrolyte with lithium metal. These layers are not clearly separated, which is contrary to what is often reported. The gradient distribution of the species within the SEI therefore corresponds to a partly mosaic structured SEI at the borders of the layers. At the lithium surface, an inorganic layer of lithium fluoride and then lithium carbonate is observed, followed by an organic, more porous SEI layer consisting of lithium ethylene dicarbonate. Simulations further reveal the strong prevalence of corrosion processes of the metal, which provide more than 99% of the lithium for the SEI reaction processes. The salt contributes less than 1% to the SEI formation. Additionally, SEI formation below and above the initial interface was observable. The here presented novel modeling approach allows an unprecedented in-depth analysis of processes during native SEI formation that can be used to improve design for high battery performance and durability.
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*Disclaimer
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License Summary*
You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
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1. Introduction
2. Methods
2.1. General Reaction Model
No. | reaction |
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A graphical illustration is provided in the SI, Scheme S1.
The lithium metal consists of pure lithium without any external impurities due to, e.g., oxidation. The electrolyte is assumed to have no impurities like water.
Lithium is always able to be oxidized spontaneously to Li+ + e–. This is assumed since a metal in contact with an electrolyte always oxidizes to a certain degree depending on its electrochemical stability. (51) This effect was also shown via MD simulations indicating that the oxidation barrier for lithium is very low. (24) Thus, lithium metal atoms can spontaneously react with species analogously as Li+.
All reactions occur at 25 °C, since the AIMD parameters were obtained at the same temperature.
Gaseous species are not modeled, as they are assumed to be inert and be removed instantaneously from the surface into the cell. Similarly, a pressure increase due to gas evolution is neglected.
The following species are considered as SEI species: (CH2OCO2Li)2, Li2CO3, Li3F, and Li4F. Their clusters are assumed to be in a solid state and are able to be part of the SEI layer on lithium metal.
2.2. MD/DFT Model
2.3. KMC Model
Figure 1
Figure 1. (a) Basic KMC box illustration. (b) Modeled processes in the KMC simulation. Reactions: The letters indicate different types of molecules. Diffusion: Movement of a molecule from one site to another. Clustering: Clusters are marked in (dark) red, nonclustered molecules are shown in blue.
2.3.1. Reaction
2.3.2. Diffusion
2.3.3. Clustering
2.3.4. Implementation and Parameter Set
parameter | variable | value | source |
---|---|---|---|
diffusion constant in EC | D | 1.8 · 10–10 m2 s–1 | chosen in the range of (59) |
diameter of molecule | d | 0.5 nm | chosen |
activation energy | Ea | see SI, Table S1 | see SI, Table S1 |
free energy | ΔrG | see SI, Table S1 | see SI, Table S1 |
initial last lithium metal layer | hll | 30 (≙10.329 nm) | chosen |
last significant tunneling layer | hmax | 34 (≙11.706 nm) | chosen |
reaction rate constant | k | calculated | eqs 5 and 6 |
frequency factor | k0 | 1013 s–1 | chosen (cf. (63)) |
lateral distance of two sites | Δl | 0.3443 nm | chosen in the range of (53) |
length of the simulation box | lx | 5.1645 nm | chosen |
width of the simulation box | ly | 5.1645 nm | chosen |
height of the simulation box | lz | 25.8225 nm | chosen |
probability of electron at last significant tunneling layer | pmax | 0.01 | chosen |
temperature | T | 298.15 K | chosen |
transition rate | W | calculated | eqs 4, 8, and 11 |
electron factor | σ | calculated | eq 7 |
2.3.5. Evaluation and Interpretation
3. Results and Discussion
3.1. SEI Growth and Species Distribution
Figure 2
Figure 2. Change of species distribution at the lithium-electrode interface due to reactions that lead to the build-up of the solid electrolyte interphase at T = 298.15 K, open circuit potential, using pure EC and cLiPF6 = 2 M. (a) Initial configuration; (b) Configuration at 102.8 ns.
Figure 3
Figure 3. Progress of the SEI formation process at T = 298.15 K and cLiPF6 = 2 M after 0.4 ns (left) and 41.4 ns (right). (a, b) KMC with distribution of selected molecules; (c, d) Volume occupied by the solid SEI species at a given height. The area between the two gray lines constitutes the solid SEI layer where clustered species are connected; (e, f) Relative occurrence of processes over height. 100% corresponds to the layer with the highest amount of the total processes occurring.
3.2. SEI Structure Analysis
Figure 4
Figure 4. Evolution of maximal and average height of SEI over time during the SEI formation process for T = 25 °C, 2 M LiPF6 in EC.
Figure 5
Figure 5. SEI volume fraction over time. (a) Overall mean SEI volume fraction. (b) Volume fraction by SEI species and lithium over height: (1) After 4.1 ns; (2) After 14.1 ns; (3) After 102.8 ns. The red dashed line separates the regions of dense and porous SEI.
4. Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.2c05898.
Reaction network, including corresponding energies and clustering processes; Molecular volume calculation; Variable step size methodology for the KMC simulation; Derivation of the electron factor; KMC boxes at different time frames and cross-sectional views; Analysis of the clustering processes and reaction rates (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
Supercomputer resources from the Texas A&M University High Performance Computer Center and Texas Advanced Computing Center (TACC) are gratefully acknowledged.
AIMD | Ab Initio Molecular Dynamics |
DFT | Density Functional Theory |
DMC | Dimethyl Carbonate |
EC | Ethylene Carbonate |
EIS | Electrochemical Impedance Spectroscopy |
KMC | Kinetic Monte Carlo |
MD | Molecular Dynamics |
SEI | Solid Electrolyte Interface |
Symbol | unit, definition |
CA | Ah·m–2, area specific capacity |
Cm | Ah·g–1, mass specific capacity |
c | mol·L–1, concentration |
d | m, diameter |
Ea | J/mol, activation energy |
G | J/mol, free energy |
h | layer number (height in z-direction) |
k | s–1, reaction constant |
k0 | s–1, frequency factor |
kb | J·K–1, Boltzmann constant |
l | m, box length |
Δl | m, distance between two lateral sites |
N | number of particles |
Na | Avogadro’s number |
probability | |
ph | fraction of a compound in the SEI at a layer height h |
pll | probability of an electron tunnelling at the layer hll |
R | J·mol–1·K–1, gas constant |
T | °C, temperature |
W | s–1, transition rate |
x | m, x coordinate |
y | m, y coordinate |
z | m, z coordinate |
Symbol | unit, definition |
η | kg·m–1·s–1, dynamic viscosity |
λ | distance variable |
ξ | random number |
ϱ | g·cm–3, density |
σ | electron factor |
Symbol | definition |
b | backward |
cl | clustering |
d | diffusion |
f | forward |
ll | last lithium layer |
r | reaction |
x | x-coordinate |
y | y-coordinate |
z | z-coordinate |
References
This article references 70 other publications.
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- 8Horstmann, B.; Shi, J.; Amine, R.; Werres, M.; He, X.; Jia, H.; Hausen, F.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Lopez, J.; Galvez-Aranda Strategies towards Enabling Lithium Metal in Batteries: Interphases and Electrodes. Energy Environ. Sci. 2021, 14 (10), 5289– 5314, DOI: 10.1039/D1EE00767JGoogle Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1Krs7bL&md5=144d78f135c3f9a3222f8a75a9bf9765Strategies towards enabling lithium metal in batteries: interphases and electrodesHorstmann, Birger; Shi, Jiayan; Amine, Rachid; Werres, Martin; He, Xin; Jia, Hao; Hausen, Florian; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Lopez, Jeffrey; Galvez-Aranda, Diego; Baakes, Florian; Bresser, Dominic; Su, Chi-Cheung; Xu, Yaobin; Xu, Wu; Jakes, Peter; Eichel, Ruediger-A.; Figgemeier, Egbert; Krewer, Ulrike; Seminario, Jorge M.; Balbuena, Perla B.; Wang, Chongmin; Passerini, Stefano; Shao-Horn, Yang; Winter, Martin; Amine, Khalil; Kostecki, Robert; Latz, ArnulfEnergy & Environmental Science (2021), 14 (10), 5289-5314CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Despite the continuous increase in capacity, lithium-ion intercalation batteries are approaching their performance limits. As a result, research is intensifying on next-generation battery technologies. The use of a lithium metal anode promises the highest theor. energy d. and enables use of lithium-free or novel high-energy cathodes. However, the lithium metal anode suffers from poor morphol. stability and Coulombic efficiency during cycling, esp. in liq. electrolytes. In contrast to solid electrolytes, liq. electrolytes have the advantage of high ionic cond. and good wetting of the anode, despite the lithium metal vol. change during cycling. Rapid capacity fade due to inhomogeneous deposition and dissoln. of lithium is the main hindrance to the successful utilization of the lithium metal anode in combination with liq. electrolytes. In this perspective, we discuss how exptl. and theor. insights can provide possible pathways for reversible cycling of two-dimensional lithium metal. Therefore, we discuss improvements in the understanding of lithium metal nucleation, deposition, and stripping on the nanoscale. As the solid-electrolyte interphase (SEI) plays a key role in the lithium morphol., we discuss how the proper SEI design might allow stable cycling. We highlight recent advances in conventional and (localized) highly concd. electrolytes in view of their resp. SEIs. We also discuss artificial interphases and three-dimensional host frameworks, which show prospects of mitigating morphol. instabilities and suppressing large shape change on the electrode level.
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- 11Xu, R.; Zhang, X. Q.; Cheng, X. B.; Peng, H. J.; Zhao, C. Z.; Yan, C.; Huang, J. Q. Artificial Soft–Rigid Protective Layer for Dendrite-Free Lithium Metal Anode. Adv. Funct Mater. 2018, 28 (8), 1705838, DOI: 10.1002/adfm.201705838Google ScholarThere is no corresponding record for this reference.
- 12Zhuang, G. v.; Ross, P. N. Analysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attentuated Total Reflection Infrared Spectroscopy. Electrochem. Solid-State Lett. 2003, 6 (7), A136– A139, DOI: 10.1149/1.1575594Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXkt1Sluro%253D&md5=d6c3596cd100caec57dc177679bee2caAnalysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attenuated Total Reflection Infrared SpectroscopyZhuang, Guorong V.; Ross, Philip N., Jr.Electrochemical and Solid-State Letters (2003), 6 (7), A136-A139CODEN: ESLEF6; ISSN:1099-0062. (Electrochemical Society)FTIR spectroscopy with attenuated total reflection geometry was used to study the surface of graphite anodes obtained from Li-ion batteries. The batteries were of the 18650-type and subjected to calender aging (60% state of charge) at 55°. The compn. of the film on an anode from a control cell (not aged) consisted of Li2C2O4, RCOOLi, and LiOMe. After aging, there was also LiOH and MeOH, and in some cases LiHCO3, probably due to the reaction of H2O with the methoxide and oxalate. There is substantial variation in the relative amts. of the 5 compds. over the surfaces of the electrodes. Alkyl carbonates may form early on, but they decomp. to more inorg. compds. with aging. The multicomponent compn. reflects the complex chem. of passive film formation in real Li-ion cells.
- 13Verma, P.; Maire, P.; Novák, P. A Review of the Features and Analyses of the Solid Electrolyte Interphase in Li-Ion Batteries. Electrochim. Acta 2010, 55 (22), 6332– 6341, DOI: 10.1016/j.electacta.2010.05.072Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtVajsbvM&md5=15e800867b70d0844c9b688e7cc3914bA review of the features and analyses of the solid electrolyte interphase in Li-ion batteriesVerma, Pallavi; Maire, Pascal; Novak, PetrElectrochimica Acta (2010), 55 (22), 6332-6341CODEN: ELCAAV; ISSN:0013-4686. (Elsevier B.V.)A review. The solid electrolyte interphase (SEI) is a protecting layer formed on the neg. electrode of Li-ion batteries as a result of electrolyte decompn., mainly during the 1st cycle. Battery performance, irreversible charge loss, rate capability, cyclability, exfoliation of graphite and safety are highly dependent on the quality of the SEI. Therefore, understanding the actual nature and compn. of SEI is of prime interest. If the chem. of the SEI formation and the manner in which each component affects battery performance are understood, SEI could be tuned to improve battery performance. In this paper key points related to the nature, formation, and features of the SEI formed on carbon neg. electrodes are discussed. SEI was analyzed by various anal. techniques amongst which FTIR and XPS are most widely used. FTIR and XPS data of SEI and its components as published by many research groups are compiled in tables for getting a global picture of what is known about the SEI. This article shall serve as a handy ref. as well as a starting point for research related to SEI.
- 14He, X.; Bresser, D.; Passerini, S.; Baakes, F.; Krewer, U.; Lopez, J.; Mallia, C. T.; Shao-Horn, Y.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Soto, F. A. The Passivity of Lithium Electrodes in Liquid Electrolytes for Secondary Batteries. Nat. Rev. Mater. 2021, 6 (11), 1036– 1052, DOI: 10.1038/s41578-021-00345-5Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitF2ksr%252FP&md5=64fc344ba7645f463d5b3d11c728668dThe passivity of lithium electrodes in liquid electrolytes for secondary batteriesHe, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, RobertNature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
- 15Baakes, F.; Lüthe, M.; Gerasimov, M.; Laue, V.; Röder, F.; Balbuena, P. B.; Krewer, U. Unveiling the Interaction of Reactions and Phase Transition during Thermal Abuse of Li-Ion Batteries. J. Power Sources 2022, 522, 230881, DOI: 10.1016/j.jpowsour.2021.230881Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1ygtrg%253D&md5=423046349bd1af1b5426d5af8e04eeceUnveiling the interaction of reactions and phase transition during thermal abuse of Li-ion batteriesBaakes, F.; Luethe, M.; Gerasimov, M.; Laue, V.; Roeder, F.; Balbuena, P. B.; Krewer, U.Journal of Power Sources (2022), 522 (), 230881CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Safety considerations have always accompanied the development of new battery chemistries; this holds esp. for the Li-ion battery with its highly reactive components. An overall assessment and decrease of risks of catastrophic failures such as during thermal runaway, requires an in-depth and quant. understanding of the ongoing processes and their interaction. This can be provided by predictive math. models. Thus, we developed a thermal runaway model that focuses on rigorous modeling of thermodn. properties and reactions of each component within a Li-ion battery. Moreover, the presented model considers vapor-liq. equil. of a binary solvent mixt. for the first time. Simulations show a fragile equil. between endothermic and exothermic reactions, such as LiPF6 and LEDC decompn., in the early phases of self-heating. Further, an autocatalytic cycle involving the prodn. of HF and the SEI component Li2CO3 could be revealed. Addnl., the unpredictability of the thermal runaway could be directly correlated to availability of LEDC or contaminants such as water. Also, solvent boiling can have a significant influence on the self-heating phase of a Li-ion battery, due to its endothermic nature. Further anal. revealed that the rising pressure, stemming from gassing reactions, can suppress solvent boiling until the thermal runaway occurs.
- 16Zhang, S. S. A Review on Electrolyte Additives for Lithium-Ion Batteries. J. Power Sources 2006, 162, 1379– 1394, DOI: 10.1016/j.jpowsour.2006.07.074Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1WmtrfL&md5=82c4a976defb060c6e4174b80ced940eA review on electrolyte additives for lithium-ion batteriesZhang, Sheng ShuiJournal of Power Sources (2006), 162 (2), 1379-1394CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A review. This paper reviews electrolyte additives used in Li-ion batteries. According to their functions, the additives can be divided into these categories: (1) solid electrolyte interface (SEI) forming improver, (2) cathode protection agent, (3) LiPF6 salt stabilizer, (4) safety protection agent, (5) Li deposition improver, and (6) other agents such as solvation enhancer, Al corrosion inhibitor, and wetting agent. The function and mechanism of each category additives are generally described and discussed.
- 17Lim, K.; Fenk, B.; Popovic, J.; Maier, J. Porosity of Solid Electrolyte Interphases on Alkali Metal Electrodes with Liquid Electrolytes. ACS Appl. Mater. Interfaces 2021, 13 (43), 51767– 51774, DOI: 10.1021/acsami.1c15607Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXit1Kqt7zO&md5=2bac528e8712951afad021b54c1b033fPorosity of Solid Electrolyte Interphases on Alkali Metal Electrodes with Liquid ElectrolytesLim, Kyungmi; Fenk, Bernhard; Popovic, Jelena; Maier, JoachimACS Applied Materials & Interfaces (2021), 13 (43), 51767-51774CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Despite the fact that solid electrolyte interphases (SEIs) on alkali metals (Li and Na) are of great importance in the utilization of batteries with high energy d., growth mechanism of SEIs under an open-circuit potential important for the shelf life and the nature of ionic transport through SEIs are yet poorly understood. In this work, SEIs on Li/Na formed by bringing the electrodes in contact with ether- and carbonate-based electrolyte in sym. cells were systematically investigated using diverse electrochem./chem. characterization techniques. Electrochem. impedance spectroscopy (EIS) measurements linked with activation energy detn. and cross-section images of Li/Na electrodes measured by ex situ FIB-SEM revealed the liq./solid composite nature of SEIs, indicating their porosity. SEIs on Na electrodes are shown to be more porous compared to the ones on Li in both carbonate and glyme-based electrolytes. Nonpassivating nature of such SEIs is detrimental for the performance of alkali metal batteries. We laid special emphasis on evaluating time-dependent activation energy using EIS.
- 18Witt, D.; Röder, F.; Krewer, U. Analysis of Lithium-Ion Battery State and Degradation via Physicochemical Cell and SEI Modeling. Batter Supercaps 2022, 5 (7), e20220006, DOI: 10.1002/batt.202200067Google ScholarThere is no corresponding record for this reference.
- 19Hao, F.; Verma, A.; Mukherjee, P. P. Mechanistic Insight into Dendrite-SEI Interactions for Lithium Metal Electrodes. J. Mater. Chem. A Mater. 2018, 6 (40), 19664– 19671, DOI: 10.1039/C8TA07997HGoogle Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVSrt7vF&md5=0eaa1a25ce4bd67cc1216035625c5e1eMechanistic insight into dendrite-SEI interactions for lithium metal electrodesHao, Feng; Verma, Ankit; Mukherjee, Partha P.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (40), 19664-19671CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The stability and homogeneity of the solid electrolyte interphase (SEI) layer are crit. toward understanding the root causes behind performance decay and safety concerns with lithium metal electrodes for energy storage. This study focuses on deducing mechanistic insights into the complexations between the Li metal electrode and SEI during electrodeposition. It is found that the formation of Li dendrite can be initiated by two distinct mechanisms: (i) aggressive Li-ion depletion near the anode-SEI interface at high reaction rates or low temp. attributed to transport limitations, and (ii) spatially varying reaction kinetics at the SEI-electrode interface due to SEI inhomogeneity even at low currents. Subsequent mech. stability analyses reveal that significantly high stress is generated due to nonuniform Li electrodeposition which could lead to crack formation in the existing SEI layer, and consequently exposure of fresh lithium to the electrolyte resulting in enhanced capacity fading. Furthermore, a non-dimensional anal. relating the interfacial stress induced failure propensity to electrochem. Biot no. and SEI heterogeneity factor is proposed, which delineates stable lithium deposition regimes.
- 20Li, Q.; Pan, H.; Li, W.; Wang, Y.; Wang, J.; Zheng, J.; Yu, X.; Li, H.; Chen, L. Homogeneous Interface Conductivity for Lithium Dendrite-Free Anode. ACS Energy Lett. 2018, 3 (9), 2259– 2266, DOI: 10.1021/acsenergylett.8b01244Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1SnsLnI&md5=d5435f19bc5a84a5753c94c90ad109b6Homogeneous Interface Conductivity for Lithium Dendrite-Free AnodeLi, Quan; Pan, Hongyi; Li, Wenjun; Wang, Yi; Wang, Junyang; Zheng, Jieyun; Yu, Xiqian; Li, Hong; Chen, LiquanACS Energy Letters (2018), 3 (9), 2259-2266CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Dendrite growth is one of the major problems that hinder the practical application of lithium metal electrodes in rechargeable lithium batteries. Herein, it is reported that the thin-film Cu3N coating can greatly suppress the lithium dendrite growth on the Cu current collector. Li|Cu and LiFePO4|Cu cells using thin-film Cu3N-modified Cu foil as electrode exhibit improved cyclic stability and low charge-discharge overpotential. A multifaceted investigation demonstrates that Cu3N can convert to Li3N/Cu nanocomposite after initial lithium plating, forming in situ a highly homogeneous conductive network. The peak-force tunneling at. force microscopy expts. enable the direct measurement of the surface cond., confirming the improved distribution uniformity for the Cu3N-modified Cu. These findings suggest that the uniformity of surface electronic cond. is an important factor for homogeneous lithium plating-stripping, and in situ formation of a nanoconductive network via conversion reaction could be an effective way to smoothen surface cond. and thus to achieve high uniformity.
- 21Harting, N.; Wolff, N.; Röder, F.; Krewer, U. Nonlinear Frequency Response Analysis (NFRA) of Lithium-Ion Batteries. Electrochim. Acta 2017, 248, 133– 139, DOI: 10.1016/j.electacta.2017.04.037Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Kgtr3P&md5=8b0e3add02ab83ad8e4fe2187d3356c1Nonlinear Frequency Response Analysis (NFRA) of Lithium-Ion BatteriesHarting, Nina; Wolff, Nicolas; Roeder, Fridolin; Krewer, UlrikeElectrochimica Acta (2017), 248 (), 133-139CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Electrochem. Impedance Spectroscopy (EIS) is the most commonly used technique for dynamic anal. of Li-ion batteries. EIS, however, limits anal. to linear contributions of the processes. For Li-ion batteries with their nonlinear electrochem. and physics, dynamics are only analyzed with regard to linear system behavior and therefore some dynamic information is not used. Nonlinear Frequency Response Anal. (NFRA) extends dynamic anal. to consider also nonlinearities. Higher excitation amplitudes are applied and higher order frequency responses Yn are measured. The spectra show distinct higher harmonic responses with strong characteristic nonlinear behavior. The authors study amplitude and temp. dependency of higher harmonic responses as well as the impact of ageing of Li-ion batteries with NFRA. By correlating NFRA and EIS, solid diffusion, reaction and ionic transport contributions at and in the SEI can be sepd. and identified. Thereby the method of NFRA is seen as an important addnl. dynamic anal. method for Li-ion batteries.
- 22Harting, N.; Schenkendorf, R.; Wolff, N.; Krewer, U. State-of-Health Identification of Lithium-Ion Batteries Based on Nonlinear Frequency Response Analysis: First Steps with Machine Learning. Applied Sciences 2018, 8, 821, DOI: 10.3390/app8050821Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVSgt7rM&md5=5e459d4ff5660d1ff0a105fb0706ccd2State-of-health identification of lithium-ion batteries based on nonlinear frequency response analysis: first steps with machine learningHarting, Nina; Schenkendorf, Rene; Wolff, Nicolas; Krewer, UlrikeApplied Sciences (2018), 8 (5), 821/1-821/14CODEN: ASPCC7; ISSN:2076-3417. (MDPI AG)In this study, we show an effective data-driven identification of the State-of-Health of Lithium-ion batteries by Nonlinear Frequency Response Anal. A degrdn. model based on support vector regression is derived from highly informative Nonlinear Frequency Response Anal. data sets. First, an ageing test of a Lithium-ion battery at 25 °C is presented and the impact of relevant ageing mechanisms on the nonlinear dynamics of the cells is analyzed. A correlation measure is used to identify the most sensitive frequency range for ageing tests. Here, the mid-frequency range from 1 Hz to 100 Hz shows the strongest correlation to Lithium-ion battery degrdn. The focus on the mid-frequency range leads to a dramatic redn. in measurement time of up to 92% compared to std. measurement protocols. Next, informative features are extd. and used to parametrise the support vector regression model for the State of Health degrdn. The performance of the degrdn. model is validated with addnl. cells and validation data sets, resp. We show that the degrdn. model accurately predicts the State of Health values. Validation data demonstrate the usefulness of the Nonlinear Frequency Response Anal. as an effective and fast State of Health identification method and as a versatile tool in the diagnosis of ageing of Lithium-ion batteries in general.
- 23Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Wei, F.; Zhang, J. G.; Zhang, Q. A Review of Solid Electrolyte Interphases on Lithium Metal Anode. Advanced Science 2016, 3, 1500213, DOI: 10.1002/advs.201500213Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC2srlsVymtw%253D%253D&md5=4e2625588d90c05dc5bf55d7bc68bd68A Review of Solid Electrolyte Interphases on Lithium Metal AnodeCheng Xin-Bing; Zhang Rui; Zhao Chen-Zi; Wei Fei; Zhang Qiang; Zhang Ji-GuangAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2016), 3 (3), 1500213 ISSN:2198-3844.Lithium metal batteries (LMBs) are among the most promising candidates of high-energy-density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex-situ-formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well-designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems.
- 24Ospina-Acevedo, F.; Guo, N.; Balbuena, P. B. Lithium Oxidation and Electrolyte Decomposition at Li-Metal/Liquid Electrolyte Interfaces. J. Mater. Chem. A Mater. 2020, 8 (33), 17036– 17055, DOI: 10.1039/D0TA05132BGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFShsrjP&md5=c985063dc6a01b64c68f4332579d5b89Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfacesOspina-Acevedo, Francisco; Guo, Ningxuan; Balbuena, Perla B.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17036-17055CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)We examine the evolution of events occurring when a Li metal surface is in contact with a 2 M soln. of a Li salt in a solvent or mixt. of solvents, via classical mol. dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidn. and electrolyte redn. along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some orgs.) is characterized. The anal. clearly reveals the details of these phys.-chem. events as a function of time, during 20 ns. The effects of the chem. of the electrolyte on Li oxidn. and dissoln. in the liq. electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF6 and LiCF3SO3, and various solvents including ethers and carbonates and mixts. of them. The kinetics and thermodn. of Li6F, the core nuclei in the LiF crystal, are studied by anal. of the MD trajectories, and via d. functional theory calcns. resp. The SEI formed in this computational expt. is the "native" film that would form upon contact of the Li foil with the liq. electrolyte. As such, this work is the first in a series of computational expts. that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.
- 25Aurbach, D. Review of Selected Electrode-Solution Interactions Which Determine the Performance of Li and Li Ion Batteries. J. Power Sources 2000, 89 (2), 206– 218, DOI: 10.1016/S0378-7753(00)00431-6Google Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXktFenu7w%253D&md5=7c6d2abf4914a6401c5e5da9992f2cc7Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteriesAurbach, D.Journal of Power Sources (2000), 89 (2), 206-218CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science S.A.)A review with 67 refs. on several phenomenol. electrode-soln. interactions which det. the performance of lithium and lithium ion batteries. This review is based on extensive studies of the behavior of Li, lithiated carbons and lithiated transition metal oxide electrodes in a wide variety of non-aq. electrolyte solns. These studies included spectroscopic measurements (FTIR, XPS, EDAX), morphol. and structural anal. (XRD, SEM, AFM) in conjunction with impedance spectroscopy, EQCM and std. electrochem. techniques. It appears that the performance of both Li, Li-C anodes and LixMOy cathodes depends on their surface chem. in solns. We address complicated surface film formation on these electrodes, which either contribute to electrode stabilization or to capacity fading due to an increase in the electrodes' impedance. Several common classical phenomena occurring in these systems are reviewed and discussed.
- 26Edström, K.; Herstedt, M.; Abraham, D. P. A New Look at the Solid Electrolyte Interphase on Graphite Anodes in Li-Ion Batteries. J. Power Sources 2006, 153 (2), 380– 384, DOI: 10.1016/j.jpowsour.2005.05.062Google ScholarThere is no corresponding record for this reference.
- 27Shiraishi, S.; Kanamura, K.; Takehara, Z. I. Influence of Initial Surface Condition of Lithium Metal Anodes on Surface Modification with HF. J. Appl. Electrochem. 1999, 29 (7), 867– 881, DOI: 10.1023/A:1003565229172Google ScholarThere is no corresponding record for this reference.
- 28Peled, E. The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems─The Solid Electrolyte Interphase Model. J. Electrochem. Soc. 1979, 126 (12), 2047, DOI: 10.1149/1.2128859Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3cXms1Knsg%253D%253D&md5=fe74ffb3fec01611647df8064745f23fThe electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems - the solid electrolyte interphase modelPeled, E.Journal of the Electrochemical Society (1979), 126 (12), 2047-51CODEN: JESOAN; ISSN:0013-4651.It is suggested that in practical nonaq. battery systems the alkali metal and alk. earth metals are always covered by a surface layer which is instantly formed by the reaction of the metal with the electrolyte. This layer which acts as an interphase between the metal and the soln., has the properties of a solid electrolyte. The corrosion rate of the metal, the mechanism of the deposition-dissoln. process, the kinetic parameters, the quality of the metal deposit, and the half-cell potential depend on the character of the solid electrolyte interphase.
- 29Owejan, J. E.; Owejan, J. P.; Decaluwe, S. C.; Dura, J. A. Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured in Situ by Neutron Reflectometry. Chem. Mater. 2012, 24 (11), 2133– 2140, DOI: 10.1021/cm3006887Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XmslKju7c%253D&md5=3fb2bcfcf1945a890b34a32fe7bc9c64Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron ReflectometryOwejan, Jeanette E.; Owejan, Jon P.; DeCaluwe, Steven C.; Dura, Joseph A.Chemistry of Materials (2012), 24 (11), 2133-2140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Li-ion batteries are made possible by the solid electrolyte interphase, SEI, a self-forming passivation layer, generated because of electrolyte instability with respect to the anode chem. potential. Ideally it offers sufficient electronic resistance to limit electrolyte decompn. to the amt. needed for its formation. However, slow continued SEI growth leads to capacity fade and increased cell resistance. Despite the SEI's crit. significance, currently structural characterization is incomplete because of the reactive and delicate nature of the SEI and the electrolyte system in which it is formed. Here the authors present, for the 1st time, in situ n reflectometry measurements of the SEI layer as function of potential in a working Li half-cell. The SEI layer after 10 and 20 CV cycles is 4.0 and 4.5 nm, resp., growing to 8.9 nm after potentiostatic holds that approximates a charge/discharge cycle. Specified data sets show uniform mixing of SEI components.
- 30Ramos-Sanchez, G.; Soto, F. A.; Martinez De La Hoz, J. M.; Liu, Z.; Mukherjee, P. P.; El-Mellouhi, F.; Seminario, J. M.; Balbuena, P. B. Computational Studies of Interfacial Reactions at Anode Materials: Initial Stages of the Solid-Electrolyte-Interphase Layer Formation. Journal of Electrochemical Energy Conversion and Storage 2016, 13 (3), 1– 10, DOI: 10.1115/1.4034412Google ScholarThere is no corresponding record for this reference.
- 31Soto, F. A.; Martinez de la Hoz, J. M.; Seminario, J. M.; Balbuena, P. B. Modeling Solid-Electrolyte Interfacial Phenomena in Silicon Anodes. Curr. Opin Chem. Eng. 2016, 13, 179– 185, DOI: 10.1016/j.coche.2016.08.017Google ScholarThere is no corresponding record for this reference.
- 32Camacho-Forero, L. E.; Smith, T. W.; Balbuena, P. B. Effects of High and Low Salt Concentration in Electrolytes at Lithium-Metal Anode Surfaces. J. Phys. Chem. C 2017, 121 (1), 182– 194, DOI: 10.1021/acs.jpcc.6b10774Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitV2ksrrK&md5=e9ada38a2010d8a72b0fec9c74b6d738Effects of High and Low Salt Concentration in Electrolytes at Lithium-Metal Anode SurfacesCamacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B.Journal of Physical Chemistry C (2017), 121 (1), 182-194CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The use of high-concn. salts in electrolyte solns. of lithium-sulfur (Li-S) batteries is beneficial for mitigating some effects such as polysulfide shuttle and dendrite growth at the Li metal anode. Such complex solns. have structural-, dynamical-, and reactivity-assocd. issues that need to be analyzed for a better understanding of the reasons behind such beneficial effects. A passivation interfacial layer known as solid-electrolyte interphase (SEI) is generated during battery cycling as a result of electron transfer from the metal anode causing electrolyte decompn. Here, using d. functional theory and ab initio mol. dynamics simulations, the authors study the salt decompn., solvation effects, interactions among intermediate products and other species, and potential components of the SEI layer as a function of chem. nature and concn. of the salt for lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) at 1 and 4 M concns. in dimethoxyethane. LiTFSI undergoes a less complete redn. and facilitates charge transfer from the anode, whereas LiFSI shows a more complete decompn. forming LiF as one of the main SEI products. The specific decompn. mechanisms of each salt clearly point to the initial SEI components and the potential main products derived from them. Very complex networks are found among the salt and solvent mols. in their attempt to maximize Li ion solvation that is quantified through the detn. of coordination nos.
- 33Martinez De La Hoz, J. M.; Soto, F. A.; Balbuena, P. B. Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li Ion Batteries. J. Phys. Chem. C 2015, 119 (13), 7060– 7068, DOI: 10.1021/acs.jpcc.5b01228Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXksVOlur0%253D&md5=4f56bbefc2986283a9d13917d50e65f0Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion BatteriesMartinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B.Journal of Physical Chemistry C (2015), 119 (13), 7060-7068CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Solid-electrolyte interphase (SEI) layers formed at the surface of Si anodes due to reductive decompn. of the electrolyte components are partially responsible of the irreversible capacity loss that neg. affects battery performance. The authors use ab initio mol. dynamics simulations to study how the electrolyte compn. including org. carbonates and LiPF6 affects such reactions. Solvent polarity defines salt dissocn., and there is a competition between salt and solvent/additive dissocn. The salt anion decomps., yielding a PF3 group and 3 F- anions. The PF3 group is relatively stable, but after some time, it decomps. nucleating on the anode surface as LiF. During anion decompn. the P atom progressively reduces finally becoming coupled to a surface atom or to fragments of the solvent/additive decompn. that takes place prior or simultaneously with the salt decompn. New pathways are found for formation of CO2 from vinylene carbonate reaction with the surface and for nucleation of Li oxide precursors.
- 34Bertolini, S.; Balbuena, P. B. Buildup of the Solid Electrolyte Interphase on Lithium-Metal Anodes: Reactive Molecular Dynamics Study. J. Phys. Chem. C 2018, 122 (20), 10783– 10791, DOI: 10.1021/acs.jpcc.8b03046Google Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXoslygu7s%253D&md5=f934a572f653624feae3c740344c3fd7Buildup of the Solid Electrolyte Interphase on Lithium-Metal Anodes: Reactive Molecular Dynamics StudyBertolini, Samuel; Balbuena, Perla B.Journal of Physical Chemistry C (2018), 122 (20), 10783-10791CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Using reactive mol. dynamics simulations, we evaluate atomistic-level interactions giving surface films on a Li-metal surface in contact with an electrolyte soln. We observe the evolution of the interfacial region and the formation of well-defined regions with varying d. and oxidn. state of Li; the penetration of electrolyte mols. and in some cases their electron transfer-driven decompn. leading to the initial formation of solid electrolyte interphase products. The simulations are done in the absence of a bias potential and using various electrolyte compns. including highly reactive solvents such as ethylene carbonate and less reactive solvents such as 1,3-dioxolane mixed with a 1 M concn. of a Li salt. The structure and oxidn. state of Li and some of the fragments are followed through the metal dissoln. process. The results are important to understand the nature of the Li-metal anode/electrolyte interface at open-circuit potential.
- 35von Kolzenberg, L.; Latz, A.; Horstmann, B. Chemo-Mechanical Model of SEI Growth on Silicon Electrode Particles. Batter Supercaps 2022, 5 (2), 1– 11, DOI: 10.1002/batt.202100216Google ScholarThere is no corresponding record for this reference.
- 36Röder, F.; Braatz, R. D.; Krewer, U. Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion Batteries. J. Electrochem. Soc. 2017, 164 (11), E3335– E3344, DOI: 10.1149/2.0241711jesGoogle Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFCltrnP&md5=57e0ab0a04aab365c4157b428998fd88Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion BatteriesRoder, Fridolin; Braatz, Richard D.; Krewer, UlrikeJournal of the Electrochemical Society (2017), 164 (11), E3335-E3344CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)A quant. description of the formation process of the solid electrolyte interface (SEI) on graphite electrodes requires the description of heterogeneous surface film growth mechanisms and continuum models. This article presents such an approach, which uses multi-scale modeling techniques to investigate multi-scale effects of the surface film growth. The model dynamically couples a macroscopic battery model with a kinetic Monte Carlo algorithm. The latter allows the study of atomistic surface reactions and heterogeneous surface film growth. The capability of this model is illustrated on an example using the common ethylene carbonate-based electrolyte in contact with a graphite electrode that features different particle radii. In this model, the atomistic configuration of the surface film structure impacts reactivity of the surface and thus the macroscopic reaction balances. The macroscopic properties impact surface current densities and overpotentials and thus surface film growth. The potential slope and charge consumption in graphite electrodes during the formation process qual. agrees with reported exptl. results.
- 37Methekar, R. N.; Northrop, P. W. C.; Chen, K.; Braatz, R. D.; Subramanian, V. R. Kinetic Monte Carlo Simulation of Surface Heterogeneity in Graphite Anodes for Lithium-Ion Batteries: Passive Layer Formation. Proceedings of the American Control Conference 2011, 158 (4), A363– A370, DOI: 10.1149/1.3548526Google ScholarThere is no corresponding record for this reference.
- 38Abbott, J. W.; Hanke, F. Kinetically Corrected Monte Carlo-Molecular Dynamics Simulations of Solid Electrolyte Interphase Growth. J. Chem. Theory Comput 2022, 18 (2), 925– 934, DOI: 10.1021/acs.jctc.1c00921Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xms1Sqtg%253D%253D&md5=3f49aa4e672bf9bb8898f0bdddc9770cKinetically Corrected Monte Carlo-Molecular Dynamics Simulations of Solid Electrolyte Interphase GrowthAbbott, Joseph W.; Hanke, FelixJournal of Chemical Theory and Computation (2022), 18 (2), 925-934CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)We present a kinetic approach to the Monte Carlo-mol. dynamics (MC-MD) method for simulating reactive liqs. using nonreactive force fields. A graphical reaction representation allows definition of reactions of arbitrary complexity, including their local solvation environment. Reaction probabilities and mol. dynamics (MD) simulation times are derived from ab initio calcns. Detailed validation is followed by studying the development of the solid electrolyte interphase (SEI) in lithium-ion batteries. We reproduce the exptl. obsd. two-layered structure on graphite, with an inorg. layer close to the anode and an outer org. layer. This structure develops via a near-shore aggregation mechanism.
- 39Sitapure, N.; Lee, H.; Ospina-Acevedo, F.; Balbuena, P. B.; Hwang, S.; Kwon, J. S. I. A Computational Approach to Characterize Formation of a Passivation Layer in Lithium Metal Anodes. AIChE J. 2021, 67, e17073, DOI: 10.1002/aic.17073Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVKku7fO&md5=e7d8a462c5284b1671541f08b32facfaA computational approach to characterize formation of a passivation layer in lithium metal anodesSitapure, Niranjan; Lee, Hyeonggeon; Ospina-Acevedo, Francisco; Balbuena, Perla B.; Hwang, Sungwon; Kwon, Joseph Sang-IIAIChE Journal (2021), 67 (1), e17073CODEN: AICEAC; ISSN:0001-1541. (John Wiley & Sons, Inc.)Li metal anode is the "Holy Grail" material of advanced Lithium-ion-batteries (LIBs). However, it is plagued by uncontrollable dendrite growth resulting in poor cycling efficiency and short-circuiting of batteries. This has spurred a plethora of research to understand the underlying mechanism of dendrite formation. While exptl. studies suggest that there are complex phys. and chem. interactions between heterogeneous solid-electrolyte interphase (SEI) and dendrite growth, most of the studies do not reveal the mechanisms triggering these interactions. To deal with this knowledge gap, a multiscale modeling framework is proposed which couples kinetic Monte Carlo and Mol. Dynamics simulations. Specifically, the model has been developed to account for heterogeneous SEI, dendrite-SEI interactions, and effect of electrolyte on Li electrodeposition and potential dendrite formation. This allows the proposed computational model to be extended to various electrolytes and SEI species and generate results consistent with previous exptl. studies.
- 40Röder, F.; Braatz, R. D.; Krewer, U. Multi-Scale Modeling of Solid Electrolyte Interface Formation in Lithium-Ion Batteries. Comput.-Aided Chem. Eng. 2016, 38, 157– 162, DOI: 10.1016/B978-0-444-63428-3.50031-XGoogle ScholarThere is no corresponding record for this reference.
- 41Röder, F.; Laue, V.; Krewer, U. Model Based Multiscale Analysis of Film Formation in Lithium-Ion Batteries. Batter Supercaps 2019, 2 (3), 248– 265, DOI: 10.1002/batt.201800107Google ScholarThere is no corresponding record for this reference.
- 42Nagaoka, M.; Suzuki, Y.; Okamoto, T.; Takenaka, N. A Hybrid MC/MD Reaction Method with Rare Event-Driving Mechanism: Atomistic Realization of 2-Chlorobutane Racemization Process in DMF Solution. Chem. Phys. Lett. 2013, 583, 80– 86, DOI: 10.1016/j.cplett.2013.08.017Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtlektLbN&md5=a0956cea3a137f545a90cac23606cebeA hybrid MC/MD reaction method with rare event-driving mechanism: Atomistic realization of 2-chlorobutane racemization process in DMF solutionNagaoka, Masataka; Suzuki, Yuichi; Okamoto, Takuya; Takenaka, NorioChemical Physics Letters (2013), 583 (), 80-86CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)The authors demonstrate a new efficient hybrid MC/MD reaction method with a rare event-driving mechanism as a practical atomistic mol. simulation of large-scale chem. reactive systems. Application of the method to (R)-2-chlorobutane mols. in DMF mols. starting in the optical pure state (100% e.e.) successfully provides such an atomistic state with ∼0% e.e., the expected purity of (R)- to (S)-enantiomers of the racemic mixt. in chem. equil. This hybrid MC/MD reaction method is promising for studies of various properties in chem. reactive systems and their stereochem. as well.
- 43Takenaka, N.; Bouibes, A.; Yamada, Y.; Nagaoka, M.; Yamada, A. Frontiers in Theoretical Analysis of Solid Electrolyte Interphase Formation Mechanism. Adv. Mater. 2021, 33 (37), 2100574, DOI: 10.1002/adma.202100574Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsl2mtbnI&md5=39efb9d412d72c106b175a5926dbd106Frontiers in Theoretical Analysis of Solid Electrolyte Interphase Formation MechanismTakenaka, Norio; Bouibes, Amine; Yamada, Yuki; Nagaoka, Masataka; Yamada, AtsuoAdvanced Materials (Weinheim, Germany) (2021), 33 (37), 2100574CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Solid electrolyte interphase (SEI) is an ion conductive yet electron-insulating layer on battery electrodes, which is formed by the reductive decompn. of electrolytes during the initial charge. The nature of the SEI significantly impacts the safety, power, and lifetime of the batteries. Hence, elucidating the formation mechanism of the SEI layer has become a top priority. Conventional theor. calcns. reveal initial elementary steps of electrolyte reductive decompn., whereas exptl. approaches mainly focus on the characterization of the formed SEI in the final form. Moreover, both theor. and exptl. methodologies could not approach intermediate or transient steps of SEI growth. A major breakthrough has recently been achieved through a novel multiscale simulation method, which has enriched the understanding of how the redn. products are aggregated near the electrode and influence the SEI morphologies. This highlights recent theor. achievements to reveal the growth mechanism and provides a clear guideline for designing a stable SEI layer for advanced batteries.
- 44Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114 (23), 11503– 11618, DOI: 10.1021/cr500003wGoogle Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVensr3N&md5=5d79be66e09915ece2c476aab47c4224Electrolytes and Interphases in Li-Ion Batteries and BeyondXu, KangChemical Reviews (Washington, DC, United States) (2014), 114 (23), 11503-11618CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review of advances in electrolytes and interphases in lithium-ion batteries.
- 45Wang, Y.; Nakamura, S.; Ue, M.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate. J. Am. Chem. Soc. 2001, 123 (47), 11708– 11718, DOI: 10.1021/ja0164529Google Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXnvFGmtbk%253D&md5=9bcfc5ec0f5991c82f421ded8a95affeTheoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: Reduction mechanisms of ethylene carbonateWang, Yixuan; Nakamura, Shinichiro; Ue, Makoto; Balbuena, Perla B.Journal of the American Chemical Society (2001), 123 (47), 11708-11718CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Reductive decompn. mechanisms for ethylene carbonate (EC) mol. in electrolyte solns. for lithium-ion batteries are comprehensively investigated by using d. functional theory. In gas phase the redn. of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron redn. processes. The presence of Li cation considerably stabilizes the EC redn. intermediates. The adiabatic electron affinities of the supermol. Li+(EC)n (n = 1-4) successively decrease with the no. of EC mols., independently of EC or Li+ being reduced. Regarding the reductive decompn. mechanism, Li+(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approx. 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene bicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compd. contg. an ester group, LiO(CH2)2CO2(CH2)2OCO2Li, then two very competitive reactions of the further redn. of the radical anion and the formation of lithium ethylene bicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compd. (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concn. dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)n; i.e., the formation of Li2CO3 is slightly more favorable at low EC concns., whereas (CH2OCO2Li)2 is favored at high EC concns. A two-electron redn. indeed takes place by a stepwise path. Regarding the compn. of the surface films resulting from solvent redn., for which expts. usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2OCO2Li, Li(CH2)2OCO2Li and Li2CO3.
- 46Soto, F. A.; Ma, Y.; Martinez De La Hoz, J. M.; Seminario, J. M.; Balbuena, P. B. Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries. Chem. Mater. 2015, 27 (23), 7990– 8000, DOI: 10.1021/acs.chemmater.5b03358Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvVCjtbbI&md5=d6c5f0081ec7e54048aa0d453b02d721Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable BatteriesSoto, Fernando A.; Ma, Yuguang; Martinez de la Hoz, Julibeth M.; Seminario, Jorge M.; Balbuena, Perla B.Chemistry of Materials (2015), 27 (23), 7990-8000CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Battery technol. is advancing rapidly with new materials and new chemistries; however, materials stability detg. battery lifetime and safety issues constitutes the main bottleneck. Electrolyte degrdn. processes triggered by electron transfer reactions taking place at electrode surfaces of rechargeable batteries result in multicomponent solid-electrolyte interphase (SEI) layers, recognized as the most crucial yet less well-understood phenomena impacting battery technol. Electrons flow via tunneling from the bare surface of neg. electrodes during initial battery charge causing electrolyte redn. reactions that lead to SEI nucleation, but the mechanisms for further growth beyond tunneling-allowed distances are not known. The 1st-principles computational studies demonstrate that radical species are responsible for the electron transfer that allows SEI layer growth once its thickness has evolved beyond the electron tunneling regime. The compn., structure, and properties of the SEI layer depend on the electrolyte, esp. on the extent to which they are able to polymerize after redn. Here the authors present a detailed study of polymn. mechanisms and propose mechanistic differences for electrolytes yielding a fast and a slow SEI growth. This new understanding leads to firm guidelines for rational electrolyte design.
- 47Tasaki, K.; Goldberg, A.; Lian, J.-J.; Walker, M.; Timmons, A.; Harris, S. J. Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents. J. Electrochem. Soc. 2009, 156 (12), A1019, DOI: 10.1149/1.3239850Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtlCmsbzN&md5=433ac8ee99379a475c1e174d35423704Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic SolventsTasaki, Ken; Goldberg, Alex; Lian, Jian-Jie; Walker, Merry; Timmons, Adam; Harris, Stephen J.Journal of the Electrochemical Society (2009), 156 (12), A1019-A1027CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The soly. of lithium salts in di-Me carbonate (DMC) found in solid electrolyte interface films was detd. The salt-DMC solns. were evapd., and the salts were transferred into water for ion cond. measurements. The salts examd. included Li2CO3, lithium oxalate [(LiCO2)2], LiF, LiOH, lithium Me carbonate (LiOCO2CH3), and lithium Et carbonate (LiOCO2C2H5). The salt molarity in DMC ranged from 9.6 × 10-4 mol/L (LiOCO2CH3) to 9 × 10-5 mol/L (Li2CO3) in the order of LiOCO2CH3 > LiOCO2C2H5 > LiOH > LiF > (LiCO2)2 > Li2CO3. XPS measurements on solid electrolyte interface films on the surface of the anode taken from a com. battery after soaking in DMC for 1 h suggested that the films can dissolve. Sep., the heat of dissoln. of the salts was calcd. from computer simulations for the same salts, including Li2O, lithium methoxide (LiOCH3), and dilithium ethylene glycol dicarbonate [(CH2OCO2Li)2:LiEDC] in both DMC and ethylene carbonate. The results from the computer simulations suggested that the order in which the salt was likely to dissolve in both DMC and ethylene carbonate was LiEDC > LiOCO2CH3 > LiOH > LiOCO2C2H5 > LiOCH3 > LiF > (LiCO2)2 > Li2CO3 > Li2O. This order agreed with the expt. in DMC within the exptl. error. Both expt. and computer simulations showed that the org. salts are more likely to dissolve in DMC than the inorg. salts. The calcns. also predicted that the salts dissolve more likely in ethylene carbonate than in DMC, in general. Moreover, the results from the study were used to discuss the capacity fading mechanism during the storage of lithium-ion batteries.
- 48Stich, M.; Göttlinger, M.; Kurniawan, M.; Schmidt, U.; Bund, A. Hydrolysis of LiPF6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous Media. J. Phys. Chem. C 2018, 122 (16), 8836– 8842, DOI: 10.1021/acs.jpcc.8b02080Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXnsF2kurg%253D&md5=0ac3ae78a56f62411f5fa6f4da0986e8Hydrolysis of LiPF6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous MediaStich, Michael; Goettlinger, Mara; Kurniawan, Mario; Schmidt, Udo; Bund, AndreasJournal of Physical Chemistry C (2018), 122 (16), 8836-8842CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The conducting salt in lithium-ion batteries, LiPF6, can react with water contaminations in the battery electrolyte, releasing HF and further potentially harmful species, which decrease the battery performance and can become a health hazard in the case of a leakage. In order to quantify the hydrolysis products of LiPF6 in a water-contaminated battery electrolyte (1 mol L-1 LiPF6 in EC/DEC) and in aq. soln., ion chromatog. (IC), coulometric Karl Fischer titrn. (cKFT), and acid-base titrn. were used on a time scale of several weeks. The results show that the nature of the hydrolysis products and the kinetics of the LiPF6 hydrolysis strongly depend on the solvent, with the main reaction products in the battery electrolyte being HF and HPO2F2. From the concn. development of reactants and products, we could gain valuable insight into the mechanism of hydrolysis and its kinetics. Since the obsd. kinetics do not follow simple rate laws, we develop a kinetic model based on a simplified hydrolysis process, which is able to explain the exptl. obsd. kinetics.
- 49Tornheim, A.; Sahore, R.; He, M.; Croy, J. R.; Zhang, Z. Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise. J. Electrochem. Soc. 2018, 165 (14), A3360– A3368, DOI: 10.1149/2.0611814jesGoogle Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitlahtLnL&md5=0877ce740e63ec92aa298ccb89b4ff3bPreformed anodes for high-voltage lithium-ion battery performance: fluorinated electrolytes, crosstalk, and the origins of impedance riseTornheim, Adam; Sahore, Ritu; He, Meinan; Croy, Jason R.; Zhang, ZhengchengJournal of the Electrochemical Society (2018), 165 (14), A3360-A3368CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Preformation of graphite electrodes, in a highly fluorinated electrolyte, show exemplary performance when incorporated into LiNi0.5Mn0.3Co0.2O2//graphite cells (NMC//Gr) contg. a traditional org. electrolyte. NMC//Gr cells, using preformed graphite electrodes, showed enhanced capacity and power retention as well as improved coulombic efficiencies. The increased performance was only obsd. with the use of specific electrolytes during the preforming step, where graphite electrodes, when preformed with the baseline org. carbonate electrolyte, did not show the same benefits. The identity of the preforming electrolyte was also obsd. to influence electrode crosstalk, where compds. generated at one electrode can affect the opposite electrode. The work herein presents both phys. and electrochem. evidence of electrode crosstalk and reveals the beneficial effect of the preforming procedure in limiting the assocd. degrdn. mechanisms thereof. The insights gained may lead to new methodologies for the design of electrochem. robust interfaces that can enable high-voltage, lithium-ion batteries.
- 50Perez Beltran, S.; Balbuena, P. B. SEI Formation Mechanisms and Li+ Dissolution in Lithium Metal Anodes: Impact of the Electrolyte Composition and the Electrolyte-to-Anode Ratio. J. Power Sources 2022, 551, 232203, DOI: 10.1016/j.jpowsour.2022.232203Google Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFyrtbvO&md5=0abd22ff4cda84a8881bfcf7810c0033SEI formation mechanisms and Li+ dissolution in lithium metal anode and impact of electrolyte composition and electrolyte-anode ratioPerez Beltran, Saul; Balbuena, Perla B.Journal of Power Sources (2022), 551 (), 232203CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A review. The lithium metal battery is one of today's most promising high-energy-d. storage devices. Its full-scale implementation depends on solving operational and safety issues intrinsic to the Li metal high reactivity leading to uncontrolled electrolyte decompn. and uneven Li deposition. In this work, we study the spontaneous formation of the solid electrolyte interphase (SEI) upon contact of Li metal with the electrolyte and describe the heterogeneous SEI morphol. features. Multiple electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), di-Me carbonate (DMC), 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are used. Findings include the description of the SEI evolution from dispersed LiO, LiS, LiN, and LiF clusters to a continuous and compact inorg. phase in which the LiO and LiF content depend on the presence of fluorine diluents. The role of the DME ether solvent helping the growth of a "wet-SEI" is compared to that of the highly unstable carbonate DMC, which decompg. into complex radical oligomers that might contribute to further electrolyte decompn. The impact of the electrolyte-anode ratio on LiFSI decompn. is highlighted. Finally, we suggest the existence of a crit. LiFSI concn. and electrolyte-anode ratio that could potentially balance the rate of electrolyte depletion and lithium consumption.
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- 56Soto, F. A.; Balbuena, P. B. Elucidating Oligomer-Surface and Oligomer-Oligomer Interactions at a Lithiated Silicon Surface. Electrochim. Acta 2016, 220, 312– 321, DOI: 10.1016/j.electacta.2016.10.082Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xhslansb7O&md5=f58966ef43abbfdfeeebd2f364e32855Elucidating Oligomer-Surface and Oligomer-Oligomer Interactions at a Lithiated Silicon SurfaceSoto, Fernando A.; Balbuena, Perla B.Electrochimica Acta (2016), 220 (), 312-321CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Solid-electrolyte interphase (SEI) layers are multicomponent films formed at the surface of electrodes in Li-ion batteries due to electrochem. instability of the electrolyte components. The properties of this film significantly affect the lifetime of the battery. Here the authors study the interaction of some electrolyte redn. products (oligomers) with a bare Li13Si4 (010) surface and a Li13Si4 (010) surface partially covered with LiF using classical Monte Carlo and d. functional theory-based methods The adsorption, charge transfer, and assocn. of oligomers on the surface are reported. Overall, the oligomers attach firmly to the surface. The authors' findings indicate that the surface-oligomer interaction dominates the stabilization of the system up to a coverage of ∼1 oligomer/nm2 and once this coverage is reached, oligomer-oligomer interactions dominate the stabilization of the porous block. Regarding assocn., Li ethylene dicarbonate (Li2EDC) tends to assoc. with the bare and partially covered surface through O.Li.O bridges. However, the assocn. mechanism varies depending on the existing nucleating products at the surface. In contrast, Li vinylene dicarbonate (Li2VDC)'s backbone is closer to the surface and exhibits a more flexible structure than the Li2EDC oligomer. This difference may further affect the compactness of the SEI layer. Aligned with the authors' previous studies, the authors also found oligomer decompn. on the surface. The authors' calcns. offer crit. information regarding the structure of electrolyte decompn. products over Si electrodes.
- 57Eyring, H. The Activated Complex in Chemical Reactions. J. Chem. Phys. 1935, 3 (2), 107, DOI: 10.1063/1.1749604Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaA2MXhs1Sksw%253D%253D&md5=48a4a9fa845d5bbafe3b249b9eb7b28eStatistical Mechanical Treatment of the Activated Complex in Chemical ReactionsEyring, HenryJournal of Chemical Physics (1935), 3 (), 107-15CODEN: JCPSA6; ISSN:0021-9606.A possible error in Eyring's recent calcns. of abs. reaction rates due to the short life and consequent unsharp quantization of the activated complex is noted. The existence of this error is made more probable by a consideration of the target area required by Eyring's equations at low temps. There is no doubt that his treatment becomes asymptotically correct at high temps.
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- 59Neuhaus, J.; Bellaire, D.; Kohns, M.; von Harbou, E.; Hasse, H. Self-Diffusion Coefficients in Solutions of Lithium Bis(Fluorosulfonyl)Imide with Dimethyl Carbonate and Ethylene Carbonate. Chem. Ing. Tech. 2019, 91 (11), 1633– 1639, DOI: 10.1002/cite.201900040Google Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVerurzP&md5=4fc50555d6fe3dd8060da41f6986fbd3Self-Diffusion Coefficients in Solutions of Lithium Bis(fluorosulfonyl)imide with Dimethyl Carbonate and Ethylene CarbonateNeuhaus, Johannes; Bellaire, Daniel; Kohns, Maximilian; von Harbou, Erik; Hasse, HansChemie Ingenieur Technik (2019), 91 (11), 1633-1639CODEN: CITEAH; ISSN:0009-286X. (Wiley-VCH Verlag GmbH & Co. KGaA)Org. solns. of lithium bis(fluorosulfonyl)imide (LiFSI) are promising electrolytes for Li-ion batteries. Information on the diffusion coeffs. of the species in these solns. is needed for battery design. Therefore, the self-diffusion coeffs. in such solns. were studied exptl. with the pulsed-field gradient NMR technique. The self-diffusion coeffs. of the ions Li+ and FSI- as well as those of the solvents were measured for LiFSI solns. in pure di-Me carbonate and ethylene carbonate as well as in mixts. of these solvents at 298 K and ambient pressure. Despite the Li+ ion being the smallest species in the soln., its self-diffusion coeff. is the lowest as a result of its strong coordination with the solvent mols.
- 60Schwoebel, R. L.; Shipsey, E. J. Step Motion on Crystal Surfaces. J. Appl. Phys. 1966, 37 (10), 3682– 3686, DOI: 10.1063/1.1707904Google Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF28XkslOrs78%253D&md5=6e30ed5ad8c0c080aa8b28477612f4e1Step motion on crystal surfacesSchwoebel, Richard L.; Shipsey, Edward J.Journal of Applied Physics (1966), 37 (10), 3682-6CODEN: JAPIAU; ISSN:0021-8979.Steps on crystal surfaces capture atoms diffusing on the surface with certain probabilities and, in addn., the capture probability depends on the direction from which adsorbed atoms approach the step. A general solution for the time-dependent step distribution is obtained in terms of these probabilities and an arbitrary initial distribution of an infinite sequence of parallel steps. Coalescence of steps or stabilization of step spacings can occur as a consequence of assuming that capture probabilities are directionally dependent. Some of the implications of the theoretical model are related to the growth of real crystal surfaces.
- 61Jansen, A. P. J. An Introduction To Monte Carlo Simulations Of Surface Reactions; Springer: New York, 2003.Google ScholarThere is no corresponding record for this reference.
- 62Andersson, A. M.; Henningson, A.; Siegbahn, H.; Jansson, U.; Edström, K. Electrochemically Lithiated Graphite Characterised by Photoelectron Spectroscopy. J. Power Sources 2003, 119–121, 522– 527, DOI: 10.1016/S0378-7753(03)00277-5Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXktlOntbs%253D&md5=8bbb967f6f80aff0ced0422a0874c4dcElectrochemically lithiated graphite characterised by photoelectron spectroscopyAndersson, A. M.; Henningson, A.; Siegbahn, H.; Jansson, U.; Edstrom, K.Journal of Power Sources (2003), 119-121 (), 522-527CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)XPS has been used to study the depth profile of the solid-electrolyte interphase (SEI) formed on a graphite powder electrode in a Li-ion battery. The morphol. of the SEI-layer, formed in a 1 M LiBF4 EC/DMC 2:1 soln., consists of a 900 Å porous layer of polymers (polyethylene oxide) and a 15-20 Å thin layer of Li2CO3 and LiBF4 redn.-decompn. products. Embedded LiF crystals as large as 0.2 μm were found in the polymer matrix. LiOH and Li2O are not major components on the surface but rather are found as a consequence of sputter-related reactions. Monochromatised Al Kα XPS-anal. based on the calibration of Ar+ ion sputtering of model compds. combined with a depth profile anal. based on energy tuning of synchrotron XPS can describe the highly complex compn. and morphol. of the SEI-layer.
- 63Westley, F.; United States National Bureau of Standards; National Measurement Laboratory (U.S.). Table of Recommended Rate Constants for Chemical Reactions Occurring in Combustion; United States Government Printing Office: Washington D.C., 1980.Google ScholarThere is no corresponding record for this reference.
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- 65Reniers, J. M.; Mulder, G.; Howey, D. A. Review and Performance Comparison of Mechanical-Chemical Degradation Models for Lithium-Ion Batteries. J. Electrochem. Soc. 2019, 166 (14), A3189– A3200, DOI: 10.1149/2.0281914jesGoogle ScholarThere is no corresponding record for this reference.
- 66von Kolzenberg, L.; Latz, A.; Horstmann, B. Solid–Electrolyte Interphase During Battery Cycling: Theory of Growth Regimes. ChemSusChem 2020, 13 (15), 3901– 3910, DOI: 10.1002/cssc.202000867Google Scholar66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtlSitLbP&md5=43ee64b71c0745cbe5e61d152029fd97Solid-Electrolyte Interphase During Battery Cycling: Theory of Growth Regimesvon Kolzenberg, Lars; Latz, Arnulf; Horstmann, BirgerChemSusChem (2020), 13 (15), 3901-3910CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)The capacity fade of modern lithium ion batteries is mainly caused by the formation and growth of the solid-electrolyte interphase (SEI). Numerous continuum models support its understanding and mitigation by studying SEI growth during battery storage. However, only a few electrochem. models discuss SEI growth during battery operation. In this article, a continuum model is developed that consistently captures the influence of open-circuit potential, current direction, current magnitude, and cycle no. on the growth of the SEI. The model is based on the formation and diffusion of neutral lithium atoms, which carry electrons through the SEI. Recent short- and long-term expts. provide validation for our model. SEI growth is limited by either reaction, diffusion, or migration. For the first time, the transition between these mechanisms is modelled. Thereby, an explanation is provided for the fading of capacity with time t of the form tβ with the scaling coefficent β, 0≤β≤1. Based on the model, crit. operation conditions accelerating SEI growth are identified.
- 67Liu, Z.; Lu, P.; Zhang, Q.; Xiao, X.; Qi, Y.; Chen, L. Q. A Bottom-Up Formation Mechanism of Solid Electrolyte Interphase Revealed by Isotope-Assisted Time-of-Flight Secondary Ion Mass Spectrometry. J. Phys. Chem. Lett. 2018, 9 (18), 5508– 5514, DOI: 10.1021/acs.jpclett.8b02350Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1ygtrrP&md5=7e9c7966be518a3a33bd6ddcec640e4fA Bottom-Up Formation Mechanism of Solid Electrolyte Interphase Revealed by Isotope-Assisted Time-of-Flight Secondary Ion Mass SpectrometryLiu, Zhe; Lu, Peng; Zhang, Qinglin; Xiao, Xingcheng; Qi, Yue; Chen, Long-QingJournal of Physical Chemistry Letters (2018), 9 (18), 5508-5514CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)Understanding the solid electrolyte interphase (SEI) formation mechanism is critically important for the performance and durability of lithium-ion batteries. However, the details of how SEI builds up into a nanometer-thick layer from mol. level redn. reactions on neg. electrodes are missing. Here, isotope-assisted time-of-flight secondary ion mass spectrometry analyses were designed to answer this fundamental question. By investigating the isotope ratio profile in SEI during the initial SEI formation cycle, it is discovered that the topmost SEI near the electrolyte formed first and the SEI near the electrode formed later. This new "bottom-up" SEI growth mechanism was then correlated to the electrolyte one-electron and two-electron redn. reaction dynamics, which in turn explains the formation of the two-layered org.-inorg. SEI composite structure.
- 68Lin, Y. X.; Liu, Z.; Leung, K.; Chen, L. Q.; Lu, P.; Qi, Y. Connecting the Irreversible Capacity Loss in Li-Ion Batteries with the Electronic Insulating Properties of Solid Electrolyte Interphase (SEI) Components. J. Power Sources 2016, 309, 221– 230, DOI: 10.1016/j.jpowsour.2016.01.078Google Scholar68https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xisl2ht74%253D&md5=a50d77f6dd390461f0bffc1b74f3c5d8Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) componentsLin, Yu-Xiao; Liu, Zhe; Leung, Kevin; Chen, Long-Qing; Lu, Peng; Qi, YueJournal of Power Sources (2016), 309 (), 221-230CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, resp. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by d. function theory (DFT) approaches. Based on electron tunneling theory, it is estd. that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the av. distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An anal. model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of neg. electrodes. The agreement between the model predictions and exptl. results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.
- 69Wang, A.; Kadam, S.; Li, H.; Shi, S.; Qi, Y. Review on Modeling of the Anode Solid Electrolyte Interphase (SEI) for Lithium-Ion Batteries. NPJ. Comput. Mater. 2018, 4, 15, DOI: 10.1038/s41524-018-0064-0Google ScholarThere is no corresponding record for this reference.
- 70Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and Challenges in Enabling the Lithium Metal Electrode for High-Energy and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3 (1), 16– 21, DOI: 10.1038/s41560-017-0047-2Google Scholar70https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVehurY%253D&md5=569e6865fb3a225323353f9e9f39fddbStatus and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteriesAlbertus, Paul; Babinec, Susan; Litzelman, Scott; Newman, AronNature Energy (2018), 3 (1), 16-21CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Enabling the reversible lithium metal electrode is essential for surpassing the energy content of today's lithium-ion cells. Although lithium metal cells for niche applications have been developed already, efforts are underway to create rechargeable lithium metal batteries that can significantly advance vehicle electrification and grid energy storage. In this Perspective, we focus on three tasks to guide and further advance the reversible lithium metal electrode. First, we summarize the state of research and com. efforts in terms of four key performance parameters, and identify addnl. performance parameters of interest. We then advocate for the use of limited lithium (≤30 μm) to ensure early identification of tech. challenges assocd. with stable and dendrite-free cycling and a more rapid transition to com. relevant designs. Finally, we provide a cost target and outline material costs and manufg. methods that could allow lithium metal cells to reach 100 US$ kWh-1.
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Abstract
Figure 1
Figure 1. (a) Basic KMC box illustration. (b) Modeled processes in the KMC simulation. Reactions: The letters indicate different types of molecules. Diffusion: Movement of a molecule from one site to another. Clustering: Clusters are marked in (dark) red, nonclustered molecules are shown in blue.
Figure 2
Figure 2. Change of species distribution at the lithium-electrode interface due to reactions that lead to the build-up of the solid electrolyte interphase at T = 298.15 K, open circuit potential, using pure EC and cLiPF6 = 2 M. (a) Initial configuration; (b) Configuration at 102.8 ns.
Figure 3
Figure 3. Progress of the SEI formation process at T = 298.15 K and cLiPF6 = 2 M after 0.4 ns (left) and 41.4 ns (right). (a, b) KMC with distribution of selected molecules; (c, d) Volume occupied by the solid SEI species at a given height. The area between the two gray lines constitutes the solid SEI layer where clustered species are connected; (e, f) Relative occurrence of processes over height. 100% corresponds to the layer with the highest amount of the total processes occurring.
Figure 4
Figure 4. Evolution of maximal and average height of SEI over time during the SEI formation process for T = 25 °C, 2 M LiPF6 in EC.
Figure 5
Figure 5. SEI volume fraction over time. (a) Overall mean SEI volume fraction. (b) Volume fraction by SEI species and lithium over height: (1) After 4.1 ns; (2) After 14.1 ns; (3) After 102.8 ns. The red dashed line separates the regions of dense and porous SEI.
References
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- 1Cheng, X. B.; Zhang, Q. Dendrite-Free Lithium Metal Anodes: Stable Solid Electrolyte Interphases for High-Efficiency Batteries. J. Mater. Chem. A Mater. 2015, 3 (14), 7207– 7209, DOI: 10.1039/C5TA00689A1https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXjs1OrurY%253D&md5=d8f474948bc52f3e5109916536841e7eDendrite-free lithium metal anodes: stable solid electrolyte interphases for high-efficiency batteriesCheng, Xin-Bing; Zhang, QiangJournal of Materials Chemistry A: Materials for Energy and Sustainability (2015), 3 (14), 7207-7209CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Li metal anodes are the Holy Grail of energy storage systems and they showed significant advances recently. A more superior cycling stability and a higher use ratio of the Li metal anode have been achieved by additive- and nanostructure-stabilized SEI layers. A profound understanding of the compn., internal structure, and evolution of the SEI film sheds new light on dendrite-free high-efficiency Li metal batteries.
- 2Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev. 2017, 117 (15), 10403– 10473, DOI: 10.1021/acs.chemrev.7b001152https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1eku7bK&md5=f83e2bc869af2a2d65226611e96c8227Toward Safe Lithium Metal Anode in Rechargeable Batteries: A ReviewCheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi; Zhang, QiangChemical Reviews (Washington, DC, United States) (2017), 117 (15), 10403-10473CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review is presented. The lithium metal battery is strongly considered to be one of the most promising candidates for high-energy-d. energy storage devices in our modern and technol.-based society. However, uncontrollable lithium dendrite growth induces poor cycling efficiency and severe safety concerns, dragging lithium metal batteries out of practical applications. This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth. First, the working principles and tech. challenges of a lithium metal anode are underscored. Specific attention is paid to the mechanistic understandings and quant. models for solid electrolyte interphase (SEI) formation, lithium dendrite nucleation, and growth. On the basis of previous theor. understanding and anal., recently proposed strategies to suppress dendrite growth of lithium metal anode and some other metal anodes are reviewed. A section dedicated to the potential of full-cell lithium metal batteries for practical applications is included. A general conclusion and a perspective on the current limitations and recommended future research directions of lithium metal batteries are presented. The review concludes with an attempt at summarizing the theor. and exptl. achievements in lithium metal anodes and endeavors to realize the practical applications of lithium metal batteries.
- 3Selis, L. A.; Seminario, J. M. Dendrite Formation in Li-Metal Anodes: An Atomistic Molecular Dynamics Study. RSC Adv. 2019, 9 (48), 27835– 27848, DOI: 10.1039/C9RA05067A3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs12ru7jL&md5=c753ea4e38387679093266d3cdff394eDendrite formation in Li-metal anodes: an atomistic molecular dynamics studySelis, Luis A.; Seminario, Jorge M.RSC Advances (2019), 9 (48), 27835-27848CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Lithium-metal is a desired material for anodes of Li-ion and beyond Li-ion batteries because of its large theor. specific capacity of 3860 mA h g-1 (the highest known so far), low d., and extremely low potential. Unfortunately, there are several problems that restrict the practical application of lithium-metal anodes, such as the formation of dendrites and reactivity with electrolytes. We present here a study of lithium dendrite formation on a Li-metal anode covered by a cracked solid electrolyte interface (SEI) of LiF in contact with a typical liq. electrolyte composed of 1 M LiPF6 salt solvated in ethylene carbonate. The study uses classical mol. dynamics on a model nanobattery. We tested three ways to charge the nanobattery: (1) const. current at a rate of one Li+ per 0.4 ps, (2) pulse train 10 Li+ per 4 ps, and (3) const. no. ions in the electrolyte: one Li+ enters the electrolyte from the cathode as one Li+ exits the electrolyte to the anode. We found that although the SEI does not interfere with the lithiation, the mere presence of a crack in the SEI boosts and guides dendrite formation at temps. between 325 K and 410.7 K at any C-rate, being more favorable at 325 K than at 410.7 K. On the other hand, we find that a higher C-rate (2.2C) favors the lithium dendrite formation compared to a lower C-rate (1.6C). Thus the battery could store more energy in a safe way at a lower C-rate.
- 4Tikekar, M. D.; Choudhury, S.; Tu, Z.; Archer, L. A. Design Principles for Electrolytes and Interfaces for Stable Lithium-Metal Batteries. Nat. Energy 2016, 1 (9), 16114, DOI: 10.1038/nenergy.2016.1144https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVersL8%253D&md5=3627028eaacfbf47fd2a8691cfddcef1Design principles for electrolytes and interfaces for stable lithium-metal batteriesTikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan; Archer, Lynden A.Nature Energy (2016), 1 (9), 16114CODEN: NEANFD; ISSN:2058-7546. (Nature Publishing Group)A review. The future of electrochem. energy storage hinges on the advancement of science and technol. that enables rechargeable batteries that utilize reactive metals as anodes. With specific capacity more than ten times that of the LiC6 anode used in present-day lithium-ion batteries, cells based on Li-metal anodes are of particular interest. Effective strategies for stabilizing the anode in such cells are now understood to be a requirement for progress on exceptional storage technologies, including Li-S and Li-O2 batteries. Multiple challenges-parasitic reactions of Li-metal with liq. electrolytes, unstable and dendritic electrodeposition, and dendrite-induced short circuits-derailed early efforts to commercialize such lithium-metal batteries. Here we consider approaches for rationally designing electrolytes and Li-metal/electrolyte interfaces for stable, dendrite-free operation of lithium-metal batteries. On the basis of fundamental understanding of the failure modes of reactive metal anodes, we discuss the key variables that govern the stability of electrodeposition at the Li anode and propose a universal framework for designing stable electrolytes and interfaces for lithium-metal batteries.
- 5Liu, B.; Zhang, J. G.; Xu, W. Advancing Lithium Metal Batteries. Joule 2018, 2 (5), 833– 845, DOI: 10.1016/j.joule.2018.03.0085https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVSmtLjL&md5=f461c67c4f4bd6b555451b424f2e8d7cAdvancing Lithium Metal BatteriesLiu, Bin; Zhang, Ji-Guang; Xu, WuJoule (2018), 2 (5), 833-845CODEN: JOULBR; ISSN:2542-4351. (Cell Press)Considering the limited energy d. of traditional graphite-anode-based lithium (Li)-ion batteries, alternative high-capacity anodes are greatly needed for the next-generation high-energy-d. battery systems. In this regard, Li metal is well known to be one of the most promising anodes due to its ultrahigh capacity (3,860 mAh g-1) and the very low std. neg. electrochem. potential (-3.040 V). However, dendrite growth and high reactivity of Li metal anodes result in low cycling efficiency and severe safety concerns. The recent revival of research and development on Li metal anodes has brought new, in-depth understanding and key exptl. progress toward Li metal protection and enhanced performance of Li metal batteries. In this Perspective, we concisely review recent discoveries in this field and suggest possible new research directions for further development of Li metal batteries.
- 6Lin, D.; Liu, Y.; Pei, A.; Cui, Y. Nanoscale Perspective: Materials Designs and Understandings in Lithium Metal Anodes. Nano Res. 2017, 10 (12), 4003– 4026, DOI: 10.1007/s12274-017-1596-16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXos1aksb0%253D&md5=070260b7eb7ce9a274cca40d0d6e946cNanoscale perspective: Materials designs and understandings in lithium metal anodesLin, Dingchang; Liu, Yayuan; Pei, Allen; Cui, YiNano Research (2017), 10 (12), 4003-4026CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)A review. Li metal chem. is a promising alternative with a much higher energy d. than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technol. from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies on nanoscale Li nucleation/deposition. Finally, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technol. and inspires more research in the future. [Figure not available: see fulltext.].
- 7Peled, E. Film Forming Reaction at the Lithium/Electrolyte Interface. J. Power Sources 1983, 9 (3), 253– 266, DOI: 10.1016/0378-7753(83)87026-87https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXktVyhs7s%253D&md5=612e5e5969678e1e097a6e2f935d2b7eFilm forming reaction at the lithium/electrolyte interfacePeled, E.Journal of Power Sources (1983), 9 (3-4), 253-66CODEN: JPSODZ; ISSN:0378-7753.A review with 33 refs. The topics discussed are: the deposition-dissoln. mechanism and the kinetics of solid electrolyte interphase (SEI) electrodes, the effect of several parameters on the resistivity of the SEI, the growth rate of the SEI, the morphol. of the overall passivating layer, and the voltage delay problem. Passivating layer formation and its effects on the electrochem. behavior of Li and on the performance of primary and secondary batteries are described.
- 8Horstmann, B.; Shi, J.; Amine, R.; Werres, M.; He, X.; Jia, H.; Hausen, F.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Lopez, J.; Galvez-Aranda Strategies towards Enabling Lithium Metal in Batteries: Interphases and Electrodes. Energy Environ. Sci. 2021, 14 (10), 5289– 5314, DOI: 10.1039/D1EE00767J8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1Krs7bL&md5=144d78f135c3f9a3222f8a75a9bf9765Strategies towards enabling lithium metal in batteries: interphases and electrodesHorstmann, Birger; Shi, Jiayan; Amine, Rachid; Werres, Martin; He, Xin; Jia, Hao; Hausen, Florian; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Lopez, Jeffrey; Galvez-Aranda, Diego; Baakes, Florian; Bresser, Dominic; Su, Chi-Cheung; Xu, Yaobin; Xu, Wu; Jakes, Peter; Eichel, Ruediger-A.; Figgemeier, Egbert; Krewer, Ulrike; Seminario, Jorge M.; Balbuena, Perla B.; Wang, Chongmin; Passerini, Stefano; Shao-Horn, Yang; Winter, Martin; Amine, Khalil; Kostecki, Robert; Latz, ArnulfEnergy & Environmental Science (2021), 14 (10), 5289-5314CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Despite the continuous increase in capacity, lithium-ion intercalation batteries are approaching their performance limits. As a result, research is intensifying on next-generation battery technologies. The use of a lithium metal anode promises the highest theor. energy d. and enables use of lithium-free or novel high-energy cathodes. However, the lithium metal anode suffers from poor morphol. stability and Coulombic efficiency during cycling, esp. in liq. electrolytes. In contrast to solid electrolytes, liq. electrolytes have the advantage of high ionic cond. and good wetting of the anode, despite the lithium metal vol. change during cycling. Rapid capacity fade due to inhomogeneous deposition and dissoln. of lithium is the main hindrance to the successful utilization of the lithium metal anode in combination with liq. electrolytes. In this perspective, we discuss how exptl. and theor. insights can provide possible pathways for reversible cycling of two-dimensional lithium metal. Therefore, we discuss improvements in the understanding of lithium metal nucleation, deposition, and stripping on the nanoscale. As the solid-electrolyte interphase (SEI) plays a key role in the lithium morphol., we discuss how the proper SEI design might allow stable cycling. We highlight recent advances in conventional and (localized) highly concd. electrolytes in view of their resp. SEIs. We also discuss artificial interphases and three-dimensional host frameworks, which show prospects of mitigating morphol. instabilities and suppressing large shape change on the electrode level.
- 9Fang, C.; Wang, X.; Meng, Y. S. Key Issues Hindering a Practical Lithium-Metal Anode. Trends Chem. 2019, 1 (2), 152– 158, DOI: 10.1016/j.trechm.2019.02.0159https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1CqtL%252FI&md5=8f1d37ca897fec6d66daf093461ff951Key Issues Hindering a Practical Lithium-Metal AnodeFang, Chengcheng; Wang, Xuefeng; Meng, Ying ShirleyTrends in Chemistry (2019), 1 (2), 152-158CODEN: TCRHBQ; ISSN:2589-5974. (Cell Press)The sluggish progress of battery technologies has drastically hindered the rapid development of elec. vehicles and next-generation portable electronics. The lithium (Li) metal anode is crit. to break the energy-d. bottleneck of current Li-ion chem. After being intensively studied in recent years, the Li-metal field has developed new understanding and made unprecedented progress in preventing Li-dendrite growth and improving Coulombic efficiency, esp. through development of advanced electrolytes and novel anal. tools. In this Opinion, we revisit the controversial issues surrounding Li metal as an anode based upon recent advances, revealing the underlying cause of Li-metal failure and the true role of 'solid electrolyte interphase' in Li-metal anodes. Finally, we propose future directions that must be taken in order for Li-metal batteries to become com. viable.
- 10An, S. J.; Li, J.; Daniel, C.; Mohanty, D.; Nagpure, S.; Wood, D. L. The State of Understanding of the Lithium-Ion-Battery Graphite Solid Electrolyte Interphase (SEI) and Its Relationship to Formation Cycling. Carbon N Y 2016, 105, 52– 76, DOI: 10.1016/j.carbon.2016.04.008There is no corresponding record for this reference.
- 11Xu, R.; Zhang, X. Q.; Cheng, X. B.; Peng, H. J.; Zhao, C. Z.; Yan, C.; Huang, J. Q. Artificial Soft–Rigid Protective Layer for Dendrite-Free Lithium Metal Anode. Adv. Funct Mater. 2018, 28 (8), 1705838, DOI: 10.1002/adfm.201705838There is no corresponding record for this reference.
- 12Zhuang, G. v.; Ross, P. N. Analysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attentuated Total Reflection Infrared Spectroscopy. Electrochem. Solid-State Lett. 2003, 6 (7), A136– A139, DOI: 10.1149/1.157559412https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXkt1Sluro%253D&md5=d6c3596cd100caec57dc177679bee2caAnalysis of the Chemical Composition of the Passive Film on Li-Ion Battery Anodes Using Attenuated Total Reflection Infrared SpectroscopyZhuang, Guorong V.; Ross, Philip N., Jr.Electrochemical and Solid-State Letters (2003), 6 (7), A136-A139CODEN: ESLEF6; ISSN:1099-0062. (Electrochemical Society)FTIR spectroscopy with attenuated total reflection geometry was used to study the surface of graphite anodes obtained from Li-ion batteries. The batteries were of the 18650-type and subjected to calender aging (60% state of charge) at 55°. The compn. of the film on an anode from a control cell (not aged) consisted of Li2C2O4, RCOOLi, and LiOMe. After aging, there was also LiOH and MeOH, and in some cases LiHCO3, probably due to the reaction of H2O with the methoxide and oxalate. There is substantial variation in the relative amts. of the 5 compds. over the surfaces of the electrodes. Alkyl carbonates may form early on, but they decomp. to more inorg. compds. with aging. The multicomponent compn. reflects the complex chem. of passive film formation in real Li-ion cells.
- 13Verma, P.; Maire, P.; Novák, P. A Review of the Features and Analyses of the Solid Electrolyte Interphase in Li-Ion Batteries. Electrochim. Acta 2010, 55 (22), 6332– 6341, DOI: 10.1016/j.electacta.2010.05.07213https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtVajsbvM&md5=15e800867b70d0844c9b688e7cc3914bA review of the features and analyses of the solid electrolyte interphase in Li-ion batteriesVerma, Pallavi; Maire, Pascal; Novak, PetrElectrochimica Acta (2010), 55 (22), 6332-6341CODEN: ELCAAV; ISSN:0013-4686. (Elsevier B.V.)A review. The solid electrolyte interphase (SEI) is a protecting layer formed on the neg. electrode of Li-ion batteries as a result of electrolyte decompn., mainly during the 1st cycle. Battery performance, irreversible charge loss, rate capability, cyclability, exfoliation of graphite and safety are highly dependent on the quality of the SEI. Therefore, understanding the actual nature and compn. of SEI is of prime interest. If the chem. of the SEI formation and the manner in which each component affects battery performance are understood, SEI could be tuned to improve battery performance. In this paper key points related to the nature, formation, and features of the SEI formed on carbon neg. electrodes are discussed. SEI was analyzed by various anal. techniques amongst which FTIR and XPS are most widely used. FTIR and XPS data of SEI and its components as published by many research groups are compiled in tables for getting a global picture of what is known about the SEI. This article shall serve as a handy ref. as well as a starting point for research related to SEI.
- 14He, X.; Bresser, D.; Passerini, S.; Baakes, F.; Krewer, U.; Lopez, J.; Mallia, C. T.; Shao-Horn, Y.; Cekic-Laskovic, I.; Wiemers-Meyer, S.; Soto, F. A. The Passivity of Lithium Electrodes in Liquid Electrolytes for Secondary Batteries. Nat. Rev. Mater. 2021, 6 (11), 1036– 1052, DOI: 10.1038/s41578-021-00345-514https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXitF2ksr%252FP&md5=64fc344ba7645f463d5b3d11c728668dThe passivity of lithium electrodes in liquid electrolytes for secondary batteriesHe, Xin; Bresser, Dominic; Passerini, Stefano; Baakes, Florian; Krewer, Ulrike; Lopez, Jeffrey; Mallia, Christopher Thomas; Shao-Horn, Yang; Cekic-Laskovic, Isidora; Wiemers-Meyer, Simon; Soto, Fernando A.; Ponce, Victor; Seminario, Jorge M.; Balbuena, Perla B.; Jia, Hao; Xu, Wu; Xu, Yaobin; Wang, Chongmin; Horstmann, Birger; Amine, Rachid; Su, Chi-Cheung; Shi, Jiayan; Amine, Khalil; Winter, Martin; Latz, Arnulf; Kostecki, RobertNature Reviews Materials (2021), 6 (11), 1036-1052CODEN: NRMADL; ISSN:2058-8437. (Nature Portfolio)Abstr.: Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decompn. and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liq. electrolyte interface. The formation of a passivation film (i.e., a solid electrolyte interphase) dets. ionic diffusion and the structural and morphol. evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chem. reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochem. stripping and plating of Li during battery operation. Finally, we discuss solns. to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chem., cell engineering and the intrinsic instability of the Li metal-electrolyte interface.
- 15Baakes, F.; Lüthe, M.; Gerasimov, M.; Laue, V.; Röder, F.; Balbuena, P. B.; Krewer, U. Unveiling the Interaction of Reactions and Phase Transition during Thermal Abuse of Li-Ion Batteries. J. Power Sources 2022, 522, 230881, DOI: 10.1016/j.jpowsour.2021.23088115https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1ygtrg%253D&md5=423046349bd1af1b5426d5af8e04eeceUnveiling the interaction of reactions and phase transition during thermal abuse of Li-ion batteriesBaakes, F.; Luethe, M.; Gerasimov, M.; Laue, V.; Roeder, F.; Balbuena, P. B.; Krewer, U.Journal of Power Sources (2022), 522 (), 230881CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)Safety considerations have always accompanied the development of new battery chemistries; this holds esp. for the Li-ion battery with its highly reactive components. An overall assessment and decrease of risks of catastrophic failures such as during thermal runaway, requires an in-depth and quant. understanding of the ongoing processes and their interaction. This can be provided by predictive math. models. Thus, we developed a thermal runaway model that focuses on rigorous modeling of thermodn. properties and reactions of each component within a Li-ion battery. Moreover, the presented model considers vapor-liq. equil. of a binary solvent mixt. for the first time. Simulations show a fragile equil. between endothermic and exothermic reactions, such as LiPF6 and LEDC decompn., in the early phases of self-heating. Further, an autocatalytic cycle involving the prodn. of HF and the SEI component Li2CO3 could be revealed. Addnl., the unpredictability of the thermal runaway could be directly correlated to availability of LEDC or contaminants such as water. Also, solvent boiling can have a significant influence on the self-heating phase of a Li-ion battery, due to its endothermic nature. Further anal. revealed that the rising pressure, stemming from gassing reactions, can suppress solvent boiling until the thermal runaway occurs.
- 16Zhang, S. S. A Review on Electrolyte Additives for Lithium-Ion Batteries. J. Power Sources 2006, 162, 1379– 1394, DOI: 10.1016/j.jpowsour.2006.07.07416https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28Xht1WmtrfL&md5=82c4a976defb060c6e4174b80ced940eA review on electrolyte additives for lithium-ion batteriesZhang, Sheng ShuiJournal of Power Sources (2006), 162 (2), 1379-1394CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A review. This paper reviews electrolyte additives used in Li-ion batteries. According to their functions, the additives can be divided into these categories: (1) solid electrolyte interface (SEI) forming improver, (2) cathode protection agent, (3) LiPF6 salt stabilizer, (4) safety protection agent, (5) Li deposition improver, and (6) other agents such as solvation enhancer, Al corrosion inhibitor, and wetting agent. The function and mechanism of each category additives are generally described and discussed.
- 17Lim, K.; Fenk, B.; Popovic, J.; Maier, J. Porosity of Solid Electrolyte Interphases on Alkali Metal Electrodes with Liquid Electrolytes. ACS Appl. Mater. Interfaces 2021, 13 (43), 51767– 51774, DOI: 10.1021/acsami.1c1560717https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXit1Kqt7zO&md5=2bac528e8712951afad021b54c1b033fPorosity of Solid Electrolyte Interphases on Alkali Metal Electrodes with Liquid ElectrolytesLim, Kyungmi; Fenk, Bernhard; Popovic, Jelena; Maier, JoachimACS Applied Materials & Interfaces (2021), 13 (43), 51767-51774CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)Despite the fact that solid electrolyte interphases (SEIs) on alkali metals (Li and Na) are of great importance in the utilization of batteries with high energy d., growth mechanism of SEIs under an open-circuit potential important for the shelf life and the nature of ionic transport through SEIs are yet poorly understood. In this work, SEIs on Li/Na formed by bringing the electrodes in contact with ether- and carbonate-based electrolyte in sym. cells were systematically investigated using diverse electrochem./chem. characterization techniques. Electrochem. impedance spectroscopy (EIS) measurements linked with activation energy detn. and cross-section images of Li/Na electrodes measured by ex situ FIB-SEM revealed the liq./solid composite nature of SEIs, indicating their porosity. SEIs on Na electrodes are shown to be more porous compared to the ones on Li in both carbonate and glyme-based electrolytes. Nonpassivating nature of such SEIs is detrimental for the performance of alkali metal batteries. We laid special emphasis on evaluating time-dependent activation energy using EIS.
- 18Witt, D.; Röder, F.; Krewer, U. Analysis of Lithium-Ion Battery State and Degradation via Physicochemical Cell and SEI Modeling. Batter Supercaps 2022, 5 (7), e20220006, DOI: 10.1002/batt.202200067There is no corresponding record for this reference.
- 19Hao, F.; Verma, A.; Mukherjee, P. P. Mechanistic Insight into Dendrite-SEI Interactions for Lithium Metal Electrodes. J. Mater. Chem. A Mater. 2018, 6 (40), 19664– 19671, DOI: 10.1039/C8TA07997H19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVSrt7vF&md5=0eaa1a25ce4bd67cc1216035625c5e1eMechanistic insight into dendrite-SEI interactions for lithium metal electrodesHao, Feng; Verma, Ankit; Mukherjee, Partha P.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2018), 6 (40), 19664-19671CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The stability and homogeneity of the solid electrolyte interphase (SEI) layer are crit. toward understanding the root causes behind performance decay and safety concerns with lithium metal electrodes for energy storage. This study focuses on deducing mechanistic insights into the complexations between the Li metal electrode and SEI during electrodeposition. It is found that the formation of Li dendrite can be initiated by two distinct mechanisms: (i) aggressive Li-ion depletion near the anode-SEI interface at high reaction rates or low temp. attributed to transport limitations, and (ii) spatially varying reaction kinetics at the SEI-electrode interface due to SEI inhomogeneity even at low currents. Subsequent mech. stability analyses reveal that significantly high stress is generated due to nonuniform Li electrodeposition which could lead to crack formation in the existing SEI layer, and consequently exposure of fresh lithium to the electrolyte resulting in enhanced capacity fading. Furthermore, a non-dimensional anal. relating the interfacial stress induced failure propensity to electrochem. Biot no. and SEI heterogeneity factor is proposed, which delineates stable lithium deposition regimes.
- 20Li, Q.; Pan, H.; Li, W.; Wang, Y.; Wang, J.; Zheng, J.; Yu, X.; Li, H.; Chen, L. Homogeneous Interface Conductivity for Lithium Dendrite-Free Anode. ACS Energy Lett. 2018, 3 (9), 2259– 2266, DOI: 10.1021/acsenergylett.8b0124420https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1SnsLnI&md5=d5435f19bc5a84a5753c94c90ad109b6Homogeneous Interface Conductivity for Lithium Dendrite-Free AnodeLi, Quan; Pan, Hongyi; Li, Wenjun; Wang, Yi; Wang, Junyang; Zheng, Jieyun; Yu, Xiqian; Li, Hong; Chen, LiquanACS Energy Letters (2018), 3 (9), 2259-2266CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)Dendrite growth is one of the major problems that hinder the practical application of lithium metal electrodes in rechargeable lithium batteries. Herein, it is reported that the thin-film Cu3N coating can greatly suppress the lithium dendrite growth on the Cu current collector. Li|Cu and LiFePO4|Cu cells using thin-film Cu3N-modified Cu foil as electrode exhibit improved cyclic stability and low charge-discharge overpotential. A multifaceted investigation demonstrates that Cu3N can convert to Li3N/Cu nanocomposite after initial lithium plating, forming in situ a highly homogeneous conductive network. The peak-force tunneling at. force microscopy expts. enable the direct measurement of the surface cond., confirming the improved distribution uniformity for the Cu3N-modified Cu. These findings suggest that the uniformity of surface electronic cond. is an important factor for homogeneous lithium plating-stripping, and in situ formation of a nanoconductive network via conversion reaction could be an effective way to smoothen surface cond. and thus to achieve high uniformity.
- 21Harting, N.; Wolff, N.; Röder, F.; Krewer, U. Nonlinear Frequency Response Analysis (NFRA) of Lithium-Ion Batteries. Electrochim. Acta 2017, 248, 133– 139, DOI: 10.1016/j.electacta.2017.04.03721https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXht1Kgtr3P&md5=8b0e3add02ab83ad8e4fe2187d3356c1Nonlinear Frequency Response Analysis (NFRA) of Lithium-Ion BatteriesHarting, Nina; Wolff, Nicolas; Roeder, Fridolin; Krewer, UlrikeElectrochimica Acta (2017), 248 (), 133-139CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Electrochem. Impedance Spectroscopy (EIS) is the most commonly used technique for dynamic anal. of Li-ion batteries. EIS, however, limits anal. to linear contributions of the processes. For Li-ion batteries with their nonlinear electrochem. and physics, dynamics are only analyzed with regard to linear system behavior and therefore some dynamic information is not used. Nonlinear Frequency Response Anal. (NFRA) extends dynamic anal. to consider also nonlinearities. Higher excitation amplitudes are applied and higher order frequency responses Yn are measured. The spectra show distinct higher harmonic responses with strong characteristic nonlinear behavior. The authors study amplitude and temp. dependency of higher harmonic responses as well as the impact of ageing of Li-ion batteries with NFRA. By correlating NFRA and EIS, solid diffusion, reaction and ionic transport contributions at and in the SEI can be sepd. and identified. Thereby the method of NFRA is seen as an important addnl. dynamic anal. method for Li-ion batteries.
- 22Harting, N.; Schenkendorf, R.; Wolff, N.; Krewer, U. State-of-Health Identification of Lithium-Ion Batteries Based on Nonlinear Frequency Response Analysis: First Steps with Machine Learning. Applied Sciences 2018, 8, 821, DOI: 10.3390/app805082122https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVSgt7rM&md5=5e459d4ff5660d1ff0a105fb0706ccd2State-of-health identification of lithium-ion batteries based on nonlinear frequency response analysis: first steps with machine learningHarting, Nina; Schenkendorf, Rene; Wolff, Nicolas; Krewer, UlrikeApplied Sciences (2018), 8 (5), 821/1-821/14CODEN: ASPCC7; ISSN:2076-3417. (MDPI AG)In this study, we show an effective data-driven identification of the State-of-Health of Lithium-ion batteries by Nonlinear Frequency Response Anal. A degrdn. model based on support vector regression is derived from highly informative Nonlinear Frequency Response Anal. data sets. First, an ageing test of a Lithium-ion battery at 25 °C is presented and the impact of relevant ageing mechanisms on the nonlinear dynamics of the cells is analyzed. A correlation measure is used to identify the most sensitive frequency range for ageing tests. Here, the mid-frequency range from 1 Hz to 100 Hz shows the strongest correlation to Lithium-ion battery degrdn. The focus on the mid-frequency range leads to a dramatic redn. in measurement time of up to 92% compared to std. measurement protocols. Next, informative features are extd. and used to parametrise the support vector regression model for the State of Health degrdn. The performance of the degrdn. model is validated with addnl. cells and validation data sets, resp. We show that the degrdn. model accurately predicts the State of Health values. Validation data demonstrate the usefulness of the Nonlinear Frequency Response Anal. as an effective and fast State of Health identification method and as a versatile tool in the diagnosis of ageing of Lithium-ion batteries in general.
- 23Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Wei, F.; Zhang, J. G.; Zhang, Q. A Review of Solid Electrolyte Interphases on Lithium Metal Anode. Advanced Science 2016, 3, 1500213, DOI: 10.1002/advs.20150021323https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC2srlsVymtw%253D%253D&md5=4e2625588d90c05dc5bf55d7bc68bd68A Review of Solid Electrolyte Interphases on Lithium Metal AnodeCheng Xin-Bing; Zhang Rui; Zhao Chen-Zi; Wei Fei; Zhang Qiang; Zhang Ji-GuangAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2016), 3 (3), 1500213 ISSN:2198-3844.Lithium metal batteries (LMBs) are among the most promising candidates of high-energy-density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex-situ-formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well-designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems.
- 24Ospina-Acevedo, F.; Guo, N.; Balbuena, P. B. Lithium Oxidation and Electrolyte Decomposition at Li-Metal/Liquid Electrolyte Interfaces. J. Mater. Chem. A Mater. 2020, 8 (33), 17036– 17055, DOI: 10.1039/D0TA05132B24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFShsrjP&md5=c985063dc6a01b64c68f4332579d5b89Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfacesOspina-Acevedo, Francisco; Guo, Ningxuan; Balbuena, Perla B.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (33), 17036-17055CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)We examine the evolution of events occurring when a Li metal surface is in contact with a 2 M soln. of a Li salt in a solvent or mixt. of solvents, via classical mol. dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidn. and electrolyte redn. along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some orgs.) is characterized. The anal. clearly reveals the details of these phys.-chem. events as a function of time, during 20 ns. The effects of the chem. of the electrolyte on Li oxidn. and dissoln. in the liq. electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF6 and LiCF3SO3, and various solvents including ethers and carbonates and mixts. of them. The kinetics and thermodn. of Li6F, the core nuclei in the LiF crystal, are studied by anal. of the MD trajectories, and via d. functional theory calcns. resp. The SEI formed in this computational expt. is the "native" film that would form upon contact of the Li foil with the liq. electrolyte. As such, this work is the first in a series of computational expts. that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.
- 25Aurbach, D. Review of Selected Electrode-Solution Interactions Which Determine the Performance of Li and Li Ion Batteries. J. Power Sources 2000, 89 (2), 206– 218, DOI: 10.1016/S0378-7753(00)00431-625https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3cXktFenu7w%253D&md5=7c6d2abf4914a6401c5e5da9992f2cc7Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteriesAurbach, D.Journal of Power Sources (2000), 89 (2), 206-218CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science S.A.)A review with 67 refs. on several phenomenol. electrode-soln. interactions which det. the performance of lithium and lithium ion batteries. This review is based on extensive studies of the behavior of Li, lithiated carbons and lithiated transition metal oxide electrodes in a wide variety of non-aq. electrolyte solns. These studies included spectroscopic measurements (FTIR, XPS, EDAX), morphol. and structural anal. (XRD, SEM, AFM) in conjunction with impedance spectroscopy, EQCM and std. electrochem. techniques. It appears that the performance of both Li, Li-C anodes and LixMOy cathodes depends on their surface chem. in solns. We address complicated surface film formation on these electrodes, which either contribute to electrode stabilization or to capacity fading due to an increase in the electrodes' impedance. Several common classical phenomena occurring in these systems are reviewed and discussed.
- 26Edström, K.; Herstedt, M.; Abraham, D. P. A New Look at the Solid Electrolyte Interphase on Graphite Anodes in Li-Ion Batteries. J. Power Sources 2006, 153 (2), 380– 384, DOI: 10.1016/j.jpowsour.2005.05.062There is no corresponding record for this reference.
- 27Shiraishi, S.; Kanamura, K.; Takehara, Z. I. Influence of Initial Surface Condition of Lithium Metal Anodes on Surface Modification with HF. J. Appl. Electrochem. 1999, 29 (7), 867– 881, DOI: 10.1023/A:1003565229172There is no corresponding record for this reference.
- 28Peled, E. The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems─The Solid Electrolyte Interphase Model. J. Electrochem. Soc. 1979, 126 (12), 2047, DOI: 10.1149/1.212885928https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3cXms1Knsg%253D%253D&md5=fe74ffb3fec01611647df8064745f23fThe electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems - the solid electrolyte interphase modelPeled, E.Journal of the Electrochemical Society (1979), 126 (12), 2047-51CODEN: JESOAN; ISSN:0013-4651.It is suggested that in practical nonaq. battery systems the alkali metal and alk. earth metals are always covered by a surface layer which is instantly formed by the reaction of the metal with the electrolyte. This layer which acts as an interphase between the metal and the soln., has the properties of a solid electrolyte. The corrosion rate of the metal, the mechanism of the deposition-dissoln. process, the kinetic parameters, the quality of the metal deposit, and the half-cell potential depend on the character of the solid electrolyte interphase.
- 29Owejan, J. E.; Owejan, J. P.; Decaluwe, S. C.; Dura, J. A. Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured in Situ by Neutron Reflectometry. Chem. Mater. 2012, 24 (11), 2133– 2140, DOI: 10.1021/cm300688729https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XmslKju7c%253D&md5=3fb2bcfcf1945a890b34a32fe7bc9c64Solid Electrolyte Interphase in Li-Ion Batteries: Evolving Structures Measured In situ by Neutron ReflectometryOwejan, Jeanette E.; Owejan, Jon P.; DeCaluwe, Steven C.; Dura, Joseph A.Chemistry of Materials (2012), 24 (11), 2133-2140CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Li-ion batteries are made possible by the solid electrolyte interphase, SEI, a self-forming passivation layer, generated because of electrolyte instability with respect to the anode chem. potential. Ideally it offers sufficient electronic resistance to limit electrolyte decompn. to the amt. needed for its formation. However, slow continued SEI growth leads to capacity fade and increased cell resistance. Despite the SEI's crit. significance, currently structural characterization is incomplete because of the reactive and delicate nature of the SEI and the electrolyte system in which it is formed. Here the authors present, for the 1st time, in situ n reflectometry measurements of the SEI layer as function of potential in a working Li half-cell. The SEI layer after 10 and 20 CV cycles is 4.0 and 4.5 nm, resp., growing to 8.9 nm after potentiostatic holds that approximates a charge/discharge cycle. Specified data sets show uniform mixing of SEI components.
- 30Ramos-Sanchez, G.; Soto, F. A.; Martinez De La Hoz, J. M.; Liu, Z.; Mukherjee, P. P.; El-Mellouhi, F.; Seminario, J. M.; Balbuena, P. B. Computational Studies of Interfacial Reactions at Anode Materials: Initial Stages of the Solid-Electrolyte-Interphase Layer Formation. Journal of Electrochemical Energy Conversion and Storage 2016, 13 (3), 1– 10, DOI: 10.1115/1.4034412There is no corresponding record for this reference.
- 31Soto, F. A.; Martinez de la Hoz, J. M.; Seminario, J. M.; Balbuena, P. B. Modeling Solid-Electrolyte Interfacial Phenomena in Silicon Anodes. Curr. Opin Chem. Eng. 2016, 13, 179– 185, DOI: 10.1016/j.coche.2016.08.017There is no corresponding record for this reference.
- 32Camacho-Forero, L. E.; Smith, T. W.; Balbuena, P. B. Effects of High and Low Salt Concentration in Electrolytes at Lithium-Metal Anode Surfaces. J. Phys. Chem. C 2017, 121 (1), 182– 194, DOI: 10.1021/acs.jpcc.6b1077432https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitV2ksrrK&md5=e9ada38a2010d8a72b0fec9c74b6d738Effects of High and Low Salt Concentration in Electrolytes at Lithium-Metal Anode SurfacesCamacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B.Journal of Physical Chemistry C (2017), 121 (1), 182-194CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The use of high-concn. salts in electrolyte solns. of lithium-sulfur (Li-S) batteries is beneficial for mitigating some effects such as polysulfide shuttle and dendrite growth at the Li metal anode. Such complex solns. have structural-, dynamical-, and reactivity-assocd. issues that need to be analyzed for a better understanding of the reasons behind such beneficial effects. A passivation interfacial layer known as solid-electrolyte interphase (SEI) is generated during battery cycling as a result of electron transfer from the metal anode causing electrolyte decompn. Here, using d. functional theory and ab initio mol. dynamics simulations, the authors study the salt decompn., solvation effects, interactions among intermediate products and other species, and potential components of the SEI layer as a function of chem. nature and concn. of the salt for lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) at 1 and 4 M concns. in dimethoxyethane. LiTFSI undergoes a less complete redn. and facilitates charge transfer from the anode, whereas LiFSI shows a more complete decompn. forming LiF as one of the main SEI products. The specific decompn. mechanisms of each salt clearly point to the initial SEI components and the potential main products derived from them. Very complex networks are found among the salt and solvent mols. in their attempt to maximize Li ion solvation that is quantified through the detn. of coordination nos.
- 33Martinez De La Hoz, J. M.; Soto, F. A.; Balbuena, P. B. Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li Ion Batteries. J. Phys. Chem. C 2015, 119 (13), 7060– 7068, DOI: 10.1021/acs.jpcc.5b0122833https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXksVOlur0%253D&md5=4f56bbefc2986283a9d13917d50e65f0Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion BatteriesMartinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B.Journal of Physical Chemistry C (2015), 119 (13), 7060-7068CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Solid-electrolyte interphase (SEI) layers formed at the surface of Si anodes due to reductive decompn. of the electrolyte components are partially responsible of the irreversible capacity loss that neg. affects battery performance. The authors use ab initio mol. dynamics simulations to study how the electrolyte compn. including org. carbonates and LiPF6 affects such reactions. Solvent polarity defines salt dissocn., and there is a competition between salt and solvent/additive dissocn. The salt anion decomps., yielding a PF3 group and 3 F- anions. The PF3 group is relatively stable, but after some time, it decomps. nucleating on the anode surface as LiF. During anion decompn. the P atom progressively reduces finally becoming coupled to a surface atom or to fragments of the solvent/additive decompn. that takes place prior or simultaneously with the salt decompn. New pathways are found for formation of CO2 from vinylene carbonate reaction with the surface and for nucleation of Li oxide precursors.
- 34Bertolini, S.; Balbuena, P. B. Buildup of the Solid Electrolyte Interphase on Lithium-Metal Anodes: Reactive Molecular Dynamics Study. J. Phys. Chem. C 2018, 122 (20), 10783– 10791, DOI: 10.1021/acs.jpcc.8b0304634https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXoslygu7s%253D&md5=f934a572f653624feae3c740344c3fd7Buildup of the Solid Electrolyte Interphase on Lithium-Metal Anodes: Reactive Molecular Dynamics StudyBertolini, Samuel; Balbuena, Perla B.Journal of Physical Chemistry C (2018), 122 (20), 10783-10791CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Using reactive mol. dynamics simulations, we evaluate atomistic-level interactions giving surface films on a Li-metal surface in contact with an electrolyte soln. We observe the evolution of the interfacial region and the formation of well-defined regions with varying d. and oxidn. state of Li; the penetration of electrolyte mols. and in some cases their electron transfer-driven decompn. leading to the initial formation of solid electrolyte interphase products. The simulations are done in the absence of a bias potential and using various electrolyte compns. including highly reactive solvents such as ethylene carbonate and less reactive solvents such as 1,3-dioxolane mixed with a 1 M concn. of a Li salt. The structure and oxidn. state of Li and some of the fragments are followed through the metal dissoln. process. The results are important to understand the nature of the Li-metal anode/electrolyte interface at open-circuit potential.
- 35von Kolzenberg, L.; Latz, A.; Horstmann, B. Chemo-Mechanical Model of SEI Growth on Silicon Electrode Particles. Batter Supercaps 2022, 5 (2), 1– 11, DOI: 10.1002/batt.202100216There is no corresponding record for this reference.
- 36Röder, F.; Braatz, R. D.; Krewer, U. Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion Batteries. J. Electrochem. Soc. 2017, 164 (11), E3335– E3344, DOI: 10.1149/2.0241711jes36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFCltrnP&md5=57e0ab0a04aab365c4157b428998fd88Multi-Scale Simulation of Heterogeneous Surface Film Growth Mechanisms in Lithium-Ion BatteriesRoder, Fridolin; Braatz, Richard D.; Krewer, UlrikeJournal of the Electrochemical Society (2017), 164 (11), E3335-E3344CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)A quant. description of the formation process of the solid electrolyte interface (SEI) on graphite electrodes requires the description of heterogeneous surface film growth mechanisms and continuum models. This article presents such an approach, which uses multi-scale modeling techniques to investigate multi-scale effects of the surface film growth. The model dynamically couples a macroscopic battery model with a kinetic Monte Carlo algorithm. The latter allows the study of atomistic surface reactions and heterogeneous surface film growth. The capability of this model is illustrated on an example using the common ethylene carbonate-based electrolyte in contact with a graphite electrode that features different particle radii. In this model, the atomistic configuration of the surface film structure impacts reactivity of the surface and thus the macroscopic reaction balances. The macroscopic properties impact surface current densities and overpotentials and thus surface film growth. The potential slope and charge consumption in graphite electrodes during the formation process qual. agrees with reported exptl. results.
- 37Methekar, R. N.; Northrop, P. W. C.; Chen, K.; Braatz, R. D.; Subramanian, V. R. Kinetic Monte Carlo Simulation of Surface Heterogeneity in Graphite Anodes for Lithium-Ion Batteries: Passive Layer Formation. Proceedings of the American Control Conference 2011, 158 (4), A363– A370, DOI: 10.1149/1.3548526There is no corresponding record for this reference.
- 38Abbott, J. W.; Hanke, F. Kinetically Corrected Monte Carlo-Molecular Dynamics Simulations of Solid Electrolyte Interphase Growth. J. Chem. Theory Comput 2022, 18 (2), 925– 934, DOI: 10.1021/acs.jctc.1c0092138https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xms1Sqtg%253D%253D&md5=3f49aa4e672bf9bb8898f0bdddc9770cKinetically Corrected Monte Carlo-Molecular Dynamics Simulations of Solid Electrolyte Interphase GrowthAbbott, Joseph W.; Hanke, FelixJournal of Chemical Theory and Computation (2022), 18 (2), 925-934CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)We present a kinetic approach to the Monte Carlo-mol. dynamics (MC-MD) method for simulating reactive liqs. using nonreactive force fields. A graphical reaction representation allows definition of reactions of arbitrary complexity, including their local solvation environment. Reaction probabilities and mol. dynamics (MD) simulation times are derived from ab initio calcns. Detailed validation is followed by studying the development of the solid electrolyte interphase (SEI) in lithium-ion batteries. We reproduce the exptl. obsd. two-layered structure on graphite, with an inorg. layer close to the anode and an outer org. layer. This structure develops via a near-shore aggregation mechanism.
- 39Sitapure, N.; Lee, H.; Ospina-Acevedo, F.; Balbuena, P. B.; Hwang, S.; Kwon, J. S. I. A Computational Approach to Characterize Formation of a Passivation Layer in Lithium Metal Anodes. AIChE J. 2021, 67, e17073, DOI: 10.1002/aic.1707339https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVKku7fO&md5=e7d8a462c5284b1671541f08b32facfaA computational approach to characterize formation of a passivation layer in lithium metal anodesSitapure, Niranjan; Lee, Hyeonggeon; Ospina-Acevedo, Francisco; Balbuena, Perla B.; Hwang, Sungwon; Kwon, Joseph Sang-IIAIChE Journal (2021), 67 (1), e17073CODEN: AICEAC; ISSN:0001-1541. (John Wiley & Sons, Inc.)Li metal anode is the "Holy Grail" material of advanced Lithium-ion-batteries (LIBs). However, it is plagued by uncontrollable dendrite growth resulting in poor cycling efficiency and short-circuiting of batteries. This has spurred a plethora of research to understand the underlying mechanism of dendrite formation. While exptl. studies suggest that there are complex phys. and chem. interactions between heterogeneous solid-electrolyte interphase (SEI) and dendrite growth, most of the studies do not reveal the mechanisms triggering these interactions. To deal with this knowledge gap, a multiscale modeling framework is proposed which couples kinetic Monte Carlo and Mol. Dynamics simulations. Specifically, the model has been developed to account for heterogeneous SEI, dendrite-SEI interactions, and effect of electrolyte on Li electrodeposition and potential dendrite formation. This allows the proposed computational model to be extended to various electrolytes and SEI species and generate results consistent with previous exptl. studies.
- 40Röder, F.; Braatz, R. D.; Krewer, U. Multi-Scale Modeling of Solid Electrolyte Interface Formation in Lithium-Ion Batteries. Comput.-Aided Chem. Eng. 2016, 38, 157– 162, DOI: 10.1016/B978-0-444-63428-3.50031-XThere is no corresponding record for this reference.
- 41Röder, F.; Laue, V.; Krewer, U. Model Based Multiscale Analysis of Film Formation in Lithium-Ion Batteries. Batter Supercaps 2019, 2 (3), 248– 265, DOI: 10.1002/batt.201800107There is no corresponding record for this reference.
- 42Nagaoka, M.; Suzuki, Y.; Okamoto, T.; Takenaka, N. A Hybrid MC/MD Reaction Method with Rare Event-Driving Mechanism: Atomistic Realization of 2-Chlorobutane Racemization Process in DMF Solution. Chem. Phys. Lett. 2013, 583, 80– 86, DOI: 10.1016/j.cplett.2013.08.01742https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhtlektLbN&md5=a0956cea3a137f545a90cac23606cebeA hybrid MC/MD reaction method with rare event-driving mechanism: Atomistic realization of 2-chlorobutane racemization process in DMF solutionNagaoka, Masataka; Suzuki, Yuichi; Okamoto, Takuya; Takenaka, NorioChemical Physics Letters (2013), 583 (), 80-86CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)The authors demonstrate a new efficient hybrid MC/MD reaction method with a rare event-driving mechanism as a practical atomistic mol. simulation of large-scale chem. reactive systems. Application of the method to (R)-2-chlorobutane mols. in DMF mols. starting in the optical pure state (100% e.e.) successfully provides such an atomistic state with ∼0% e.e., the expected purity of (R)- to (S)-enantiomers of the racemic mixt. in chem. equil. This hybrid MC/MD reaction method is promising for studies of various properties in chem. reactive systems and their stereochem. as well.
- 43Takenaka, N.; Bouibes, A.; Yamada, Y.; Nagaoka, M.; Yamada, A. Frontiers in Theoretical Analysis of Solid Electrolyte Interphase Formation Mechanism. Adv. Mater. 2021, 33 (37), 2100574, DOI: 10.1002/adma.20210057443https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsl2mtbnI&md5=39efb9d412d72c106b175a5926dbd106Frontiers in Theoretical Analysis of Solid Electrolyte Interphase Formation MechanismTakenaka, Norio; Bouibes, Amine; Yamada, Yuki; Nagaoka, Masataka; Yamada, AtsuoAdvanced Materials (Weinheim, Germany) (2021), 33 (37), 2100574CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Solid electrolyte interphase (SEI) is an ion conductive yet electron-insulating layer on battery electrodes, which is formed by the reductive decompn. of electrolytes during the initial charge. The nature of the SEI significantly impacts the safety, power, and lifetime of the batteries. Hence, elucidating the formation mechanism of the SEI layer has become a top priority. Conventional theor. calcns. reveal initial elementary steps of electrolyte reductive decompn., whereas exptl. approaches mainly focus on the characterization of the formed SEI in the final form. Moreover, both theor. and exptl. methodologies could not approach intermediate or transient steps of SEI growth. A major breakthrough has recently been achieved through a novel multiscale simulation method, which has enriched the understanding of how the redn. products are aggregated near the electrode and influence the SEI morphologies. This highlights recent theor. achievements to reveal the growth mechanism and provides a clear guideline for designing a stable SEI layer for advanced batteries.
- 44Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114 (23), 11503– 11618, DOI: 10.1021/cr500003w44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVensr3N&md5=5d79be66e09915ece2c476aab47c4224Electrolytes and Interphases in Li-Ion Batteries and BeyondXu, KangChemical Reviews (Washington, DC, United States) (2014), 114 (23), 11503-11618CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review of advances in electrolytes and interphases in lithium-ion batteries.
- 45Wang, Y.; Nakamura, S.; Ue, M.; Balbuena, P. B. Theoretical Studies to Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries: Reduction Mechanisms of Ethylene Carbonate. J. Am. Chem. Soc. 2001, 123 (47), 11708– 11718, DOI: 10.1021/ja016452945https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXnvFGmtbk%253D&md5=9bcfc5ec0f5991c82f421ded8a95affeTheoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: Reduction mechanisms of ethylene carbonateWang, Yixuan; Nakamura, Shinichiro; Ue, Makoto; Balbuena, Perla B.Journal of the American Chemical Society (2001), 123 (47), 11708-11718CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Reductive decompn. mechanisms for ethylene carbonate (EC) mol. in electrolyte solns. for lithium-ion batteries are comprehensively investigated by using d. functional theory. In gas phase the redn. of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron redn. processes. The presence of Li cation considerably stabilizes the EC redn. intermediates. The adiabatic electron affinities of the supermol. Li+(EC)n (n = 1-4) successively decrease with the no. of EC mols., independently of EC or Li+ being reduced. Regarding the reductive decompn. mechanism, Li+(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approx. 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene bicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compd. contg. an ester group, LiO(CH2)2CO2(CH2)2OCO2Li, then two very competitive reactions of the further redn. of the radical anion and the formation of lithium ethylene bicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compd. (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concn. dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)n; i.e., the formation of Li2CO3 is slightly more favorable at low EC concns., whereas (CH2OCO2Li)2 is favored at high EC concns. A two-electron redn. indeed takes place by a stepwise path. Regarding the compn. of the surface films resulting from solvent redn., for which expts. usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2OCO2Li, Li(CH2)2OCO2Li and Li2CO3.
- 46Soto, F. A.; Ma, Y.; Martinez De La Hoz, J. M.; Seminario, J. M.; Balbuena, P. B. Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable Batteries. Chem. Mater. 2015, 27 (23), 7990– 8000, DOI: 10.1021/acs.chemmater.5b0335846https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvVCjtbbI&md5=d6c5f0081ec7e54048aa0d453b02d721Formation and Growth Mechanisms of Solid-Electrolyte Interphase Layers in Rechargeable BatteriesSoto, Fernando A.; Ma, Yuguang; Martinez de la Hoz, Julibeth M.; Seminario, Jorge M.; Balbuena, Perla B.Chemistry of Materials (2015), 27 (23), 7990-8000CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)Battery technol. is advancing rapidly with new materials and new chemistries; however, materials stability detg. battery lifetime and safety issues constitutes the main bottleneck. Electrolyte degrdn. processes triggered by electron transfer reactions taking place at electrode surfaces of rechargeable batteries result in multicomponent solid-electrolyte interphase (SEI) layers, recognized as the most crucial yet less well-understood phenomena impacting battery technol. Electrons flow via tunneling from the bare surface of neg. electrodes during initial battery charge causing electrolyte redn. reactions that lead to SEI nucleation, but the mechanisms for further growth beyond tunneling-allowed distances are not known. The 1st-principles computational studies demonstrate that radical species are responsible for the electron transfer that allows SEI layer growth once its thickness has evolved beyond the electron tunneling regime. The compn., structure, and properties of the SEI layer depend on the electrolyte, esp. on the extent to which they are able to polymerize after redn. Here the authors present a detailed study of polymn. mechanisms and propose mechanistic differences for electrolytes yielding a fast and a slow SEI growth. This new understanding leads to firm guidelines for rational electrolyte design.
- 47Tasaki, K.; Goldberg, A.; Lian, J.-J.; Walker, M.; Timmons, A.; Harris, S. J. Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents. J. Electrochem. Soc. 2009, 156 (12), A1019, DOI: 10.1149/1.323985047https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXhtlCmsbzN&md5=433ac8ee99379a475c1e174d35423704Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic SolventsTasaki, Ken; Goldberg, Alex; Lian, Jian-Jie; Walker, Merry; Timmons, Adam; Harris, Stephen J.Journal of the Electrochemical Society (2009), 156 (12), A1019-A1027CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The soly. of lithium salts in di-Me carbonate (DMC) found in solid electrolyte interface films was detd. The salt-DMC solns. were evapd., and the salts were transferred into water for ion cond. measurements. The salts examd. included Li2CO3, lithium oxalate [(LiCO2)2], LiF, LiOH, lithium Me carbonate (LiOCO2CH3), and lithium Et carbonate (LiOCO2C2H5). The salt molarity in DMC ranged from 9.6 × 10-4 mol/L (LiOCO2CH3) to 9 × 10-5 mol/L (Li2CO3) in the order of LiOCO2CH3 > LiOCO2C2H5 > LiOH > LiF > (LiCO2)2 > Li2CO3. XPS measurements on solid electrolyte interface films on the surface of the anode taken from a com. battery after soaking in DMC for 1 h suggested that the films can dissolve. Sep., the heat of dissoln. of the salts was calcd. from computer simulations for the same salts, including Li2O, lithium methoxide (LiOCH3), and dilithium ethylene glycol dicarbonate [(CH2OCO2Li)2:LiEDC] in both DMC and ethylene carbonate. The results from the computer simulations suggested that the order in which the salt was likely to dissolve in both DMC and ethylene carbonate was LiEDC > LiOCO2CH3 > LiOH > LiOCO2C2H5 > LiOCH3 > LiF > (LiCO2)2 > Li2CO3 > Li2O. This order agreed with the expt. in DMC within the exptl. error. Both expt. and computer simulations showed that the org. salts are more likely to dissolve in DMC than the inorg. salts. The calcns. also predicted that the salts dissolve more likely in ethylene carbonate than in DMC, in general. Moreover, the results from the study were used to discuss the capacity fading mechanism during the storage of lithium-ion batteries.
- 48Stich, M.; Göttlinger, M.; Kurniawan, M.; Schmidt, U.; Bund, A. Hydrolysis of LiPF6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous Media. J. Phys. Chem. C 2018, 122 (16), 8836– 8842, DOI: 10.1021/acs.jpcc.8b0208048https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXnsF2kurg%253D&md5=0ac3ae78a56f62411f5fa6f4da0986e8Hydrolysis of LiPF6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous MediaStich, Michael; Goettlinger, Mara; Kurniawan, Mario; Schmidt, Udo; Bund, AndreasJournal of Physical Chemistry C (2018), 122 (16), 8836-8842CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)The conducting salt in lithium-ion batteries, LiPF6, can react with water contaminations in the battery electrolyte, releasing HF and further potentially harmful species, which decrease the battery performance and can become a health hazard in the case of a leakage. In order to quantify the hydrolysis products of LiPF6 in a water-contaminated battery electrolyte (1 mol L-1 LiPF6 in EC/DEC) and in aq. soln., ion chromatog. (IC), coulometric Karl Fischer titrn. (cKFT), and acid-base titrn. were used on a time scale of several weeks. The results show that the nature of the hydrolysis products and the kinetics of the LiPF6 hydrolysis strongly depend on the solvent, with the main reaction products in the battery electrolyte being HF and HPO2F2. From the concn. development of reactants and products, we could gain valuable insight into the mechanism of hydrolysis and its kinetics. Since the obsd. kinetics do not follow simple rate laws, we develop a kinetic model based on a simplified hydrolysis process, which is able to explain the exptl. obsd. kinetics.
- 49Tornheim, A.; Sahore, R.; He, M.; Croy, J. R.; Zhang, Z. Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise. J. Electrochem. Soc. 2018, 165 (14), A3360– A3368, DOI: 10.1149/2.0611814jes49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitlahtLnL&md5=0877ce740e63ec92aa298ccb89b4ff3bPreformed anodes for high-voltage lithium-ion battery performance: fluorinated electrolytes, crosstalk, and the origins of impedance riseTornheim, Adam; Sahore, Ritu; He, Meinan; Croy, Jason R.; Zhang, ZhengchengJournal of the Electrochemical Society (2018), 165 (14), A3360-A3368CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)Preformation of graphite electrodes, in a highly fluorinated electrolyte, show exemplary performance when incorporated into LiNi0.5Mn0.3Co0.2O2//graphite cells (NMC//Gr) contg. a traditional org. electrolyte. NMC//Gr cells, using preformed graphite electrodes, showed enhanced capacity and power retention as well as improved coulombic efficiencies. The increased performance was only obsd. with the use of specific electrolytes during the preforming step, where graphite electrodes, when preformed with the baseline org. carbonate electrolyte, did not show the same benefits. The identity of the preforming electrolyte was also obsd. to influence electrode crosstalk, where compds. generated at one electrode can affect the opposite electrode. The work herein presents both phys. and electrochem. evidence of electrode crosstalk and reveals the beneficial effect of the preforming procedure in limiting the assocd. degrdn. mechanisms thereof. The insights gained may lead to new methodologies for the design of electrochem. robust interfaces that can enable high-voltage, lithium-ion batteries.
- 50Perez Beltran, S.; Balbuena, P. B. SEI Formation Mechanisms and Li+ Dissolution in Lithium Metal Anodes: Impact of the Electrolyte Composition and the Electrolyte-to-Anode Ratio. J. Power Sources 2022, 551, 232203, DOI: 10.1016/j.jpowsour.2022.23220350https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFyrtbvO&md5=0abd22ff4cda84a8881bfcf7810c0033SEI formation mechanisms and Li+ dissolution in lithium metal anode and impact of electrolyte composition and electrolyte-anode ratioPerez Beltran, Saul; Balbuena, Perla B.Journal of Power Sources (2022), 551 (), 232203CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)A review. The lithium metal battery is one of today's most promising high-energy-d. storage devices. Its full-scale implementation depends on solving operational and safety issues intrinsic to the Li metal high reactivity leading to uncontrolled electrolyte decompn. and uneven Li deposition. In this work, we study the spontaneous formation of the solid electrolyte interphase (SEI) upon contact of Li metal with the electrolyte and describe the heterogeneous SEI morphol. features. Multiple electrolyte formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), di-Me carbonate (DMC), 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are used. Findings include the description of the SEI evolution from dispersed LiO, LiS, LiN, and LiF clusters to a continuous and compact inorg. phase in which the LiO and LiF content depend on the presence of fluorine diluents. The role of the DME ether solvent helping the growth of a "wet-SEI" is compared to that of the highly unstable carbonate DMC, which decompg. into complex radical oligomers that might contribute to further electrolyte decompn. The impact of the electrolyte-anode ratio on LiFSI decompn. is highlighted. Finally, we suggest the existence of a crit. LiFSI concn. and electrolyte-anode ratio that could potentially balance the rate of electrolyte depletion and lithium consumption.
- 51Hamann, C. H.; Vielstich, W. Elektrochemie, 4. Auflage.; Wiley-VCH Verlag GmbH & Co KgaA: Weinheim, 2005.There is no corresponding record for this reference.
- 52Voter, A. F. Introduction To the Kinetic Monte Carlo Method; Los Alamos, 2007. DOI: 10.1007/978-1-4020-5295-8_1 .There is no corresponding record for this reference.
- 53Doll, K.; Harrison, N. M.; Saunders, V. R. A Density Functional Study of Lithium Bulk and Surfaces. J. Phys.: Condens. Matter 1999, 11 (26), 5007– 5019, DOI: 10.1088/0953-8984/11/26/30553https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXks1aitL4%253D&md5=456499d922bd73686a4634ada7ec1e88A density functional study of lithium bulk and surfacesDoll, K.; Harrison, N. M.; Saunders, V. R.Journal of Physics: Condensed Matter (1999), 11 (26), 5007-5019CODEN: JCOMEL; ISSN:0953-8984. (Institute of Physics Publishing)We report the bulk and surface properties of lithium computed within a full-potential linear combination of Gaussian-type orbitals formalism using both d. functional theory and the Hartree-Fock approxn. We examine the convergence of computed properties with respect to numerical approxns. and also explore the use of finite-temp. d. functional theory. We demonstrate that fully converged calcns. reproduce cohesive properties, elastic consts., band structure, and surface energies in full agreement with exptl. data and, where available, previously calcns.
- 54Mortimer, C. E.; Müller, U. Chemie, 11th ed.; Thieme: Stuttgart, New York, 2014.There is no corresponding record for this reference.
- 55Kratzer, P. Monte Carlo and Kinetic Monte Carlo Methods. arXiv:0904.2556 [cond-mat.mtrl-sci] 2009, na, DOI: 10.48550/arXiv.0904.2556There is no corresponding record for this reference.
- 56Soto, F. A.; Balbuena, P. B. Elucidating Oligomer-Surface and Oligomer-Oligomer Interactions at a Lithiated Silicon Surface. Electrochim. Acta 2016, 220, 312– 321, DOI: 10.1016/j.electacta.2016.10.08256https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xhslansb7O&md5=f58966ef43abbfdfeeebd2f364e32855Elucidating Oligomer-Surface and Oligomer-Oligomer Interactions at a Lithiated Silicon SurfaceSoto, Fernando A.; Balbuena, Perla B.Electrochimica Acta (2016), 220 (), 312-321CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)Solid-electrolyte interphase (SEI) layers are multicomponent films formed at the surface of electrodes in Li-ion batteries due to electrochem. instability of the electrolyte components. The properties of this film significantly affect the lifetime of the battery. Here the authors study the interaction of some electrolyte redn. products (oligomers) with a bare Li13Si4 (010) surface and a Li13Si4 (010) surface partially covered with LiF using classical Monte Carlo and d. functional theory-based methods The adsorption, charge transfer, and assocn. of oligomers on the surface are reported. Overall, the oligomers attach firmly to the surface. The authors' findings indicate that the surface-oligomer interaction dominates the stabilization of the system up to a coverage of ∼1 oligomer/nm2 and once this coverage is reached, oligomer-oligomer interactions dominate the stabilization of the porous block. Regarding assocn., Li ethylene dicarbonate (Li2EDC) tends to assoc. with the bare and partially covered surface through O.Li.O bridges. However, the assocn. mechanism varies depending on the existing nucleating products at the surface. In contrast, Li vinylene dicarbonate (Li2VDC)'s backbone is closer to the surface and exhibits a more flexible structure than the Li2EDC oligomer. This difference may further affect the compactness of the SEI layer. Aligned with the authors' previous studies, the authors also found oligomer decompn. on the surface. The authors' calcns. offer crit. information regarding the structure of electrolyte decompn. products over Si electrodes.
- 57Eyring, H. The Activated Complex in Chemical Reactions. J. Chem. Phys. 1935, 3 (2), 107, DOI: 10.1063/1.174960457https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaA2MXhs1Sksw%253D%253D&md5=48a4a9fa845d5bbafe3b249b9eb7b28eStatistical Mechanical Treatment of the Activated Complex in Chemical ReactionsEyring, HenryJournal of Chemical Physics (1935), 3 (), 107-15CODEN: JCPSA6; ISSN:0021-9606.A possible error in Eyring's recent calcns. of abs. reaction rates due to the short life and consequent unsharp quantization of the activated complex is noted. The existence of this error is made more probable by a consideration of the target area required by Eyring's equations at low temps. There is no doubt that his treatment becomes asymptotically correct at high temps.
- 58Ibach, H. Physics of Surfaces and Interfaces; Springer Berlin: Heidelberg, 2006. DOI: 10.1007/3-540-34710-0 .There is no corresponding record for this reference.
- 59Neuhaus, J.; Bellaire, D.; Kohns, M.; von Harbou, E.; Hasse, H. Self-Diffusion Coefficients in Solutions of Lithium Bis(Fluorosulfonyl)Imide with Dimethyl Carbonate and Ethylene Carbonate. Chem. Ing. Tech. 2019, 91 (11), 1633– 1639, DOI: 10.1002/cite.20190004059https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVerurzP&md5=4fc50555d6fe3dd8060da41f6986fbd3Self-Diffusion Coefficients in Solutions of Lithium Bis(fluorosulfonyl)imide with Dimethyl Carbonate and Ethylene CarbonateNeuhaus, Johannes; Bellaire, Daniel; Kohns, Maximilian; von Harbou, Erik; Hasse, HansChemie Ingenieur Technik (2019), 91 (11), 1633-1639CODEN: CITEAH; ISSN:0009-286X. (Wiley-VCH Verlag GmbH & Co. KGaA)Org. solns. of lithium bis(fluorosulfonyl)imide (LiFSI) are promising electrolytes for Li-ion batteries. Information on the diffusion coeffs. of the species in these solns. is needed for battery design. Therefore, the self-diffusion coeffs. in such solns. were studied exptl. with the pulsed-field gradient NMR technique. The self-diffusion coeffs. of the ions Li+ and FSI- as well as those of the solvents were measured for LiFSI solns. in pure di-Me carbonate and ethylene carbonate as well as in mixts. of these solvents at 298 K and ambient pressure. Despite the Li+ ion being the smallest species in the soln., its self-diffusion coeff. is the lowest as a result of its strong coordination with the solvent mols.
- 60Schwoebel, R. L.; Shipsey, E. J. Step Motion on Crystal Surfaces. J. Appl. Phys. 1966, 37 (10), 3682– 3686, DOI: 10.1063/1.170790460https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF28XkslOrs78%253D&md5=6e30ed5ad8c0c080aa8b28477612f4e1Step motion on crystal surfacesSchwoebel, Richard L.; Shipsey, Edward J.Journal of Applied Physics (1966), 37 (10), 3682-6CODEN: JAPIAU; ISSN:0021-8979.Steps on crystal surfaces capture atoms diffusing on the surface with certain probabilities and, in addn., the capture probability depends on the direction from which adsorbed atoms approach the step. A general solution for the time-dependent step distribution is obtained in terms of these probabilities and an arbitrary initial distribution of an infinite sequence of parallel steps. Coalescence of steps or stabilization of step spacings can occur as a consequence of assuming that capture probabilities are directionally dependent. Some of the implications of the theoretical model are related to the growth of real crystal surfaces.
- 61Jansen, A. P. J. An Introduction To Monte Carlo Simulations Of Surface Reactions; Springer: New York, 2003.There is no corresponding record for this reference.
- 62Andersson, A. M.; Henningson, A.; Siegbahn, H.; Jansson, U.; Edström, K. Electrochemically Lithiated Graphite Characterised by Photoelectron Spectroscopy. J. Power Sources 2003, 119–121, 522– 527, DOI: 10.1016/S0378-7753(03)00277-562https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXktlOntbs%253D&md5=8bbb967f6f80aff0ced0422a0874c4dcElectrochemically lithiated graphite characterised by photoelectron spectroscopyAndersson, A. M.; Henningson, A.; Siegbahn, H.; Jansson, U.; Edstrom, K.Journal of Power Sources (2003), 119-121 (), 522-527CODEN: JPSODZ; ISSN:0378-7753. (Elsevier Science B.V.)XPS has been used to study the depth profile of the solid-electrolyte interphase (SEI) formed on a graphite powder electrode in a Li-ion battery. The morphol. of the SEI-layer, formed in a 1 M LiBF4 EC/DMC 2:1 soln., consists of a 900 Å porous layer of polymers (polyethylene oxide) and a 15-20 Å thin layer of Li2CO3 and LiBF4 redn.-decompn. products. Embedded LiF crystals as large as 0.2 μm were found in the polymer matrix. LiOH and Li2O are not major components on the surface but rather are found as a consequence of sputter-related reactions. Monochromatised Al Kα XPS-anal. based on the calibration of Ar+ ion sputtering of model compds. combined with a depth profile anal. based on energy tuning of synchrotron XPS can describe the highly complex compn. and morphol. of the SEI-layer.
- 63Westley, F.; United States National Bureau of Standards; National Measurement Laboratory (U.S.). Table of Recommended Rate Constants for Chemical Reactions Occurring in Combustion; United States Government Printing Office: Washington D.C., 1980.There is no corresponding record for this reference.
- 64MathWorks. MATLAB (Version R2020b, Update 2); Natick, MA, 2020.There is no corresponding record for this reference.
- 65Reniers, J. M.; Mulder, G.; Howey, D. A. Review and Performance Comparison of Mechanical-Chemical Degradation Models for Lithium-Ion Batteries. J. Electrochem. Soc. 2019, 166 (14), A3189– A3200, DOI: 10.1149/2.0281914jesThere is no corresponding record for this reference.
- 66von Kolzenberg, L.; Latz, A.; Horstmann, B. Solid–Electrolyte Interphase During Battery Cycling: Theory of Growth Regimes. ChemSusChem 2020, 13 (15), 3901– 3910, DOI: 10.1002/cssc.20200086766https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtlSitLbP&md5=43ee64b71c0745cbe5e61d152029fd97Solid-Electrolyte Interphase During Battery Cycling: Theory of Growth Regimesvon Kolzenberg, Lars; Latz, Arnulf; Horstmann, BirgerChemSusChem (2020), 13 (15), 3901-3910CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)The capacity fade of modern lithium ion batteries is mainly caused by the formation and growth of the solid-electrolyte interphase (SEI). Numerous continuum models support its understanding and mitigation by studying SEI growth during battery storage. However, only a few electrochem. models discuss SEI growth during battery operation. In this article, a continuum model is developed that consistently captures the influence of open-circuit potential, current direction, current magnitude, and cycle no. on the growth of the SEI. The model is based on the formation and diffusion of neutral lithium atoms, which carry electrons through the SEI. Recent short- and long-term expts. provide validation for our model. SEI growth is limited by either reaction, diffusion, or migration. For the first time, the transition between these mechanisms is modelled. Thereby, an explanation is provided for the fading of capacity with time t of the form tβ with the scaling coefficent β, 0≤β≤1. Based on the model, crit. operation conditions accelerating SEI growth are identified.
- 67Liu, Z.; Lu, P.; Zhang, Q.; Xiao, X.; Qi, Y.; Chen, L. Q. A Bottom-Up Formation Mechanism of Solid Electrolyte Interphase Revealed by Isotope-Assisted Time-of-Flight Secondary Ion Mass Spectrometry. J. Phys. Chem. Lett. 2018, 9 (18), 5508– 5514, DOI: 10.1021/acs.jpclett.8b0235067https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1ygtrrP&md5=7e9c7966be518a3a33bd6ddcec640e4fA Bottom-Up Formation Mechanism of Solid Electrolyte Interphase Revealed by Isotope-Assisted Time-of-Flight Secondary Ion Mass SpectrometryLiu, Zhe; Lu, Peng; Zhang, Qinglin; Xiao, Xingcheng; Qi, Yue; Chen, Long-QingJournal of Physical Chemistry Letters (2018), 9 (18), 5508-5514CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)Understanding the solid electrolyte interphase (SEI) formation mechanism is critically important for the performance and durability of lithium-ion batteries. However, the details of how SEI builds up into a nanometer-thick layer from mol. level redn. reactions on neg. electrodes are missing. Here, isotope-assisted time-of-flight secondary ion mass spectrometry analyses were designed to answer this fundamental question. By investigating the isotope ratio profile in SEI during the initial SEI formation cycle, it is discovered that the topmost SEI near the electrolyte formed first and the SEI near the electrode formed later. This new "bottom-up" SEI growth mechanism was then correlated to the electrolyte one-electron and two-electron redn. reaction dynamics, which in turn explains the formation of the two-layered org.-inorg. SEI composite structure.
- 68Lin, Y. X.; Liu, Z.; Leung, K.; Chen, L. Q.; Lu, P.; Qi, Y. Connecting the Irreversible Capacity Loss in Li-Ion Batteries with the Electronic Insulating Properties of Solid Electrolyte Interphase (SEI) Components. J. Power Sources 2016, 309, 221– 230, DOI: 10.1016/j.jpowsour.2016.01.07868https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xisl2ht74%253D&md5=a50d77f6dd390461f0bffc1b74f3c5d8Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) componentsLin, Yu-Xiao; Liu, Zhe; Leung, Kevin; Chen, Long-Qing; Lu, Peng; Qi, YueJournal of Power Sources (2016), 309 (), 221-230CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, resp. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by d. function theory (DFT) approaches. Based on electron tunneling theory, it is estd. that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the av. distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An anal. model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of neg. electrodes. The agreement between the model predictions and exptl. results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.
- 69Wang, A.; Kadam, S.; Li, H.; Shi, S.; Qi, Y. Review on Modeling of the Anode Solid Electrolyte Interphase (SEI) for Lithium-Ion Batteries. NPJ. Comput. Mater. 2018, 4, 15, DOI: 10.1038/s41524-018-0064-0There is no corresponding record for this reference.
- 70Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and Challenges in Enabling the Lithium Metal Electrode for High-Energy and Low-Cost Rechargeable Batteries. Nat. Energy 2018, 3 (1), 16– 21, DOI: 10.1038/s41560-017-0047-270https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXitVehurY%253D&md5=569e6865fb3a225323353f9e9f39fddbStatus and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteriesAlbertus, Paul; Babinec, Susan; Litzelman, Scott; Newman, AronNature Energy (2018), 3 (1), 16-21CODEN: NEANFD; ISSN:2058-7546. (Nature Research)Enabling the reversible lithium metal electrode is essential for surpassing the energy content of today's lithium-ion cells. Although lithium metal cells for niche applications have been developed already, efforts are underway to create rechargeable lithium metal batteries that can significantly advance vehicle electrification and grid energy storage. In this Perspective, we focus on three tasks to guide and further advance the reversible lithium metal electrode. First, we summarize the state of research and com. efforts in terms of four key performance parameters, and identify addnl. performance parameters of interest. We then advocate for the use of limited lithium (≤30 μm) to ensure early identification of tech. challenges assocd. with stable and dendrite-free cycling and a more rapid transition to com. relevant designs. Finally, we provide a cost target and outline material costs and manufg. methods that could allow lithium metal cells to reach 100 US$ kWh-1.
Supporting Information
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Reaction network, including corresponding energies and clustering processes; Molecular volume calculation; Variable step size methodology for the KMC simulation; Derivation of the electron factor; KMC boxes at different time frames and cross-sectional views; Analysis of the clustering processes and reaction rates (PDF)
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