Visualizing the SEI formation between lithium metal and solid-state electrolyte

Ren, Fucheng; Wu, Yuqi; Zuo, Wenhua; Zhao, Wengao; Pan, Siyuan; Lin, Hongxin; Yu, Haichuan; Lin, Jing; Lin, Min; Yao, Xiayin; Brezesinski, Torsten; Gong, Zhengliang; Yang, Yong

doi:10.1039/d3ee03536k

Title: Visualizing the SEI formation between lithium metal and solid-state electrolyte

Journal Article · 05 March 2024 · Energy & Environmental Science

DOI: https://doi.org/10.1039/d3ee03536k · OSTI ID:2497723

Ren, Fucheng ^[1]; Wu, Yuqi ^[1];

^[2];

^[3]; Pan, Siyuan ^[1]; Lin, Hongxin ^[1]; Yu, Haichuan ^[4]; Lin, Jing ^[3]; Lin, Min ^[1];

^[4];

^[3];

^[1];

^[1]

Xiamen University (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Karlsruhe Inst. of Technology (KIT) (Germany)
Chinese Academy of Sciences (CAS), Ningbo (China). Ningbo Institute of Materials Technology and Engineering

The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li₃PS₄ interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li₃PS₄. This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (~40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li₃PS₄ interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li₂S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. Finally, this information is crucial for better understanding interfacial ion mobility.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2497723

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 8 Vol. 17; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

In Situ Construction of a LiF‐Enriched Interface for Stable All‐Solid‐State Batteries and its Origin Revealed by Cryo‐TEM Sheng, Ouwei; Zheng, Jianhui; Ju, Zhijin Advanced Materials, Vol. 32, Issue 34 https://doi.org/10.1002/adma.202000223	journal	July 2020
In Situ Investigation of Lithium Metal–Solid Electrolyte Anode Interfaces with ToF‐SIMS Otto, Svenja‐K.; Riegger, Luise M.; Fuchs, Till Advanced Materials Interfaces, Vol. 9, Issue 13 https://doi.org/10.1002/admi.202102387	journal	March 2022
Self‐Healing Mechanism of Lithium in Lithium Metal Jiao, Junyu; Lai, Genming; Zhao, Liang Advanced Science, Vol. 9, Issue 12 https://doi.org/10.1002/advs.202105574	journal	February 2022
Sustained Release‐Driven Formation of Ultrastable SEI between Li ₆ PS ₅ Cl and Lithium Anode for Sulfide‐Based Solid‐State Batteries Chen, Ya; Li, Wenwen; Sun, Changzhi Advanced Energy Materials, Vol. 11, Issue 4 https://doi.org/10.1002/aenm.202002545	journal	December 2020
Recent Progress in Understanding Solid Electrolyte Interphase on Lithium Metal Anodes Wu, Haiping; Jia, Hao; Wang, Chongmin Advanced Energy Materials, Vol. 11, Issue 5 https://doi.org/10.1002/aenm.202003092	journal	December 2020
Interfacial Issues and Modification of Solid Electrolyte Interphase for Li Metal Anode in Liquid and Solid Electrolytes Chae, Oh B.; Lucht, Brett L. Advanced Energy Materials, Vol. 13, Issue 14 https://doi.org/10.1002/aenm.202203791	journal	February 2023
DeePMD-kit: A deep learning package for many-body potential energy representation and molecular dynamics Wang, Han; Zhang, Linfeng; Han, Jiequn Computer Physics Communications, Vol. 228 https://doi.org/10.1016/j.cpc.2018.03.016	journal	July 2018
An In Vivo Formed Solid Electrolyte Surface Layer Enables Stable Plating of Li Metal Pang, Quan; Liang, Xiao; Shyamsunder, Abhinandan Joule, Vol. 1, Issue 4 https://doi.org/10.1016/j.joule.2017.11.009	journal	December 2017
Computation-Accelerated Design of Materials and Interfaces for All-Solid-State Lithium-Ion Batteries Nolan, Adelaide M.; Zhu, Yizhou; He, Xingfeng Joule, Vol. 2, Issue 10 https://doi.org/10.1016/j.joule.2018.08.017	journal	October 2018
Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy Nanda, Jagjit; Yang, Guang; Hou, Tingzheng Joule, Vol. 3, Issue 8 https://doi.org/10.1016/j.joule.2019.05.026	journal	August 2019
Revealing the Impact of Space-Charge Layers on the Li-Ion Transport in All-Solid-State Batteries Cheng, Zhu; Liu, Ming; Ganapathy, Swapna Joule, Vol. 4, Issue 6 https://doi.org/10.1016/j.joule.2020.04.002	journal	June 2020
Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy Cheng, Diyi; Wynn, Thomas A.; Wang, Xuefeng Joule, Vol. 4, Issue 11 https://doi.org/10.1016/j.joule.2020.08.013	journal	November 2020
Computational study of lithium nucleation tendency in Li7La3Zr2O12 (LLZO) and rational design of interlayer materials to prevent lithium dendrites Tian, Hong-Kang; Xu, Bo; Qi, Yue Journal of Power Sources, Vol. 392 https://doi.org/10.1016/j.jpowsour.2018.04.098	journal	July 2018
Exploring interfacial stability of solid-state electrolytes at the lithium-metal anode surface Camacho-Forero, Luis E.; Balbuena, Perla B. Journal of Power Sources, Vol. 396 https://doi.org/10.1016/j.jpowsour.2018.06.092	journal	August 2018
Interfaces and interphases in batteries Xu, Kang Journal of Power Sources, Vol. 559 https://doi.org/10.1016/j.jpowsour.2023.232652	journal	March 2023
Interphase formation and degradation of charge transfer kinetics between a lithium metal anode and highly crystalline Li7P3S11 solid electrolyte Wenzel, Sebastian; Weber, Dominik A.; Leichtweiss, Thomas Solid State Ionics, Vol. 286 https://doi.org/10.1016/j.ssi.2015.11.034	journal	March 2016
Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes Wenzel, Sebastian; Sedlmaier, Stefan J.; Dietrich, Christian Solid State Ionics, Vol. 318 https://doi.org/10.1016/j.ssi.2017.07.005	journal	May 2018
XPS and SEM analysis between Li/Li3PS4 interface with Au thin film for all-solid-state lithium batteries Kato, Atsutaka; Kowada, Hiroe; Deguchi, Minako Solid State Ionics, Vol. 322 https://doi.org/10.1016/j.ssi.2018.04.011	journal	September 2018
Visualizing the Sensitive Lithium with Atomic Precision: Cryogenic Electron Microscopy for Batteries Liu, Yujing; Ju, Zhijin; Zhang, Baolin Accounts of Chemical Research, Vol. 54, Issue 9 https://doi.org/10.1021/acs.accounts.1c00120	journal	April 2021
Maintaining a Flat Li Surface during the Li Stripping Process via Interface Design Yang, Chi-Ta; Qi, Yue Chemistry of Materials, Vol. 33, Issue 8 https://doi.org/10.1021/acs.chemmater.0c04814	journal	April 2021
Instability of the Li₇SiPS₈ Solid Electrolyte at the Lithium Metal Anode and Interphase Formation Riegger, Luise M.; Otto, Svenja-K.; Sadowski, Marcel Chemistry of Materials, Vol. 34, Issue 8 https://doi.org/10.1021/acs.chemmater.1c04302	journal	April 2022
Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li ₁₀ GeP ₂ S ₁₂ at the Lithium Metal Anode Wenzel, Sebastian; Randau, Simon; Leichtweiß, Thomas Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00610	journal	March 2016
Structural and Electronic-State Changes of a Sulfide Solid Electrolyte during the Li Deinsertion–Insertion Processes Hakari, Takashi; Deguchi, Minako; Mitsuhara, Kei Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00551	journal	May 2017
Reaction and Space Charge Layer Formation at the LiCoO ₂ –LiPON Interface: Insights on Defect Formation and Ion Energy Level Alignment by a Combined Surface Science–Simulation Approach Fingerle, Mathias; Buchheit, Roman; Sicolo, Sabrina Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b00890	journal	September 2017
Electrochemical Redox Behavior of Li Ion Conducting Sulfide Solid Electrolytes Swamy, Tushar; Chen, Xinwei; Chiang, Yet-Ming Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b03420	journal	January 2019
Interfacial Electronic Properties Dictate Li Dendrite Growth in Solid Electrolytes Tian, Hong-Kang; Liu, Zhe; Ji, Yanzhou Chemistry of Materials, Vol. 31, Issue 18 https://doi.org/10.1021/acs.chemmater.9b01967	journal	August 2019
Elucidating Interfacial Phenomena between Solid-State Electrolytes and the Sulfur-Cathode of Lithium–Sulfur Batteries Camacho-Forero, Luis E.; Balbuena, Perla B. Chemistry of Materials, Vol. 32, Issue 1 https://doi.org/10.1021/acs.chemmater.9b03880	journal	November 2019
Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes Banerjee, Abhik; Wang, Xuefeng; Fang, Chengcheng Chemical Reviews, Vol. 120, Issue 14 https://doi.org/10.1021/acs.chemrev.0c00101	journal	June 2020
Physicochemical Concepts of the Lithium Metal Anode in Solid-State Batteries Krauskopf, Thorben; Richter, Felix H.; Zeier, Wolfgang G. Chemical Reviews, Vol. 120, Issue 15 https://doi.org/10.1021/acs.chemrev.0c00431	journal	July 2020
Thermodynamically Consistent Model for Space-Charge-Layer Formation in a Solid Electrolyte Braun, Stefanie; Yada, Chihiro; Latz, Arnulf The Journal of Physical Chemistry C, Vol. 119, Issue 39 https://doi.org/10.1021/acs.jpcc.5b02679	journal	September 2015
Atomic to Nanoscale Origin of Vinylene Carbonate Enhanced Cycling Stability of Lithium Metal Anode Revealed by Cryo-Transmission Electron Microscopy Xu, Yaobin; Wu, Haiping; He, Yang Nano Letters, Vol. 20, Issue 1 https://doi.org/10.1021/acs.nanolett.9b04111	journal	December 2019
Analysis of Diffusion in Solid-State Electrolytes through MD Simulations, Improvement of the Li-Ion Conductivity in β-Li ₃ PS ₄ as an Example de Klerk, Niek J. J.; van der Maas, Eveline; Wagemaker, Marnix ACS Applied Energy Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsaem.8b00457	journal	June 2018
Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na ₃ PS ₄ and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries Wenzel, Sebastian; Leichtweiss, Thomas; Weber, Dominik A. ACS Applied Materials & Interfaces, Vol. 8, Issue 41 https://doi.org/10.1021/acsami.6b10119	journal	October 2016
Guidelines for All-Solid-State Battery Design and Electrode Buffer Layers Based on Chemical Potential Profile Calculation Nakamura, Takashi; Amezawa, Koji; Kulisch, Jörn ACS Applied Materials & Interfaces, Vol. 11, Issue 22 https://doi.org/10.1021/acsami.9b03053	journal	May 2019
Stack Pressure Measurements to Probe the Evolution of the Lithium–Solid-State Electrolyte Interface Lee, Chanhee; Han, Sang Yun; Lewis, John A. ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01395	journal	August 2021
Nanostructure of the Interphase Layer between a Single Li Dendrite and Sulfide Electrolyte in All-Solid-State Li Batteries Luo, Shuting; Liu, Xinyu; Zhang, Xiao ACS Energy Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsenergylett.2c01543	journal	August 2022
Interphases and Electrode Crosstalk Dictate the Thermal Stability of Solid-State Batteries Vishnugopi, Bairav S.; Hasan, Md Toukir; Zhou, Hanwei ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02443	journal	December 2022
Quantum Mechanics Reactive Dynamics Study of Solid Li-Electrode/Li ₆ PS ₅ Cl-Electrolyte Interface Cheng, Tao; Merinov, Boris V.; Morozov, Sergey ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00319	journal	May 2017
Elucidating Reversible Electrochemical Redox of Li ₆ PS ₅ Cl Solid Electrolyte Tan, Darren H. S.; Wu, Erik A.; Nguyen, Han ACS Energy Letters, Vol. 4, Issue 10 https://doi.org/10.1021/acsenergylett.9b01693	journal	August 2019
Impact of the Local Environment on Li Ion Transport in Inorganic Components of Solid Electrolyte Interphases Hu, Taiping; Tian, Jianxin; Dai, Fuzhi Journal of the American Chemical Society, Vol. 145, Issue 2 https://doi.org/10.1021/jacs.2c11521	journal	December 2022
Switching of Redox Levels Leads to High Reductive Stability in Water-in-Salt Electrolytes Wang, Feng; Sun, Yan; Cheng, Jun Journal of the American Chemical Society, Vol. 145, Issue 7 https://doi.org/10.1021/jacs.2c11793	journal	February 2023
The Mixing Mechanism during Lithiation of Si Negative Electrode in Li-Ion Batteries: An Ab Initio Molecular Dynamics Study Johari, Priya; Qi, Yue; Shenoy, Vivek B. Nano Letters, Vol. 11, Issue 12 https://doi.org/10.1021/nl203302d	journal	December 2011
Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes Wood, Kevin N.; Steirer, K. Xerxes; Hafner, Simon E. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04762-z	journal	June 2018
In-situ visualization of the space-charge-layer effect on interfacial lithium-ion transport in all-solid-state batteries Wang, Longlong; Xie, Ruicong; Chen, Bingbing Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19726-5	journal	November 2020
Effect of current density on the solid electrolyte interphase formation at the lithium∣Li6PS5Cl interface Narayanan, Sudarshan; Ulissi, Ulderico; Gibson, Joshua S. Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-34855-9	journal	November 2022
Lithium crystallization at solid interfaces Yang, Menghao; Liu, Yunsheng; Mo, Yifei Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-38757-2	journal	May 2023
Challenges in speeding up solid-state battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 8, Issue 3 https://doi.org/10.1038/s41560-023-01208-9	journal	February 2023
Characterization of the structure and chemistry of the solid–electrolyte interface by cryo-EM leads to high-performance solid-state Li-metal batteries Lin, Ruoqian; He, Yubin; Wang, Chunyang Nature Nanotechnology, Vol. 17, Issue 7 https://doi.org/10.1038/s41565-022-01148-7	journal	June 2022
Imaging solid–electrolyte interphase dynamics using operando reflection interference microscopy Feng, Guangxia; Jia, Hao; Shi, Yaping Nature Nanotechnology https://doi.org/10.1038/s41565-023-01316-3	journal	February 2023
Modeling the electrical double layer at solid-state electrochemical interfaces Swift, Michael W.; Swift, James W.; Qi, Yue Nature Computational Science, Vol. 1, Issue 3 https://doi.org/10.1038/s43588-021-00041-y	journal	March 2021
Spectroscopic characterization of lithium thiophosphates by XPS and XAS – a model to help monitor interfacial reactions in all-solid-state batteries Dietrich, Christian; Koerver, Raimund; Gaultois, Michael W. Physical Chemistry Chemical Physics, Vol. 20, Issue 30 https://doi.org/10.1039/C8CP01968A	journal	January 2018
Chemo-mechanical expansion of lithium electrode materials – on the route to mechanically optimized all-solid-state batteries Koerver, Raimund; Zhang, Wenbo; de Biasi, Lea Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE00907D	journal	January 2018
Pressure effects on sulfide electrolytes for all solid-state batteries Doux, Jean-Marie; Yang, Yangyuchen; Tan, Darren H. S. Journal of Materials Chemistry A, Vol. 8, Issue 10 https://doi.org/10.1039/C9TA12889A	journal	January 2020
Deep potentials for materials science Wen, Tongqi; Zhang, Linfeng; Wang, Han Materials Futures, Vol. 1, Issue 2 https://doi.org/10.1088/2752-5724/ac681d	journal	May 2022
Modeling interfaces between solids: Application to Li battery materials Lepley, N. D.; Holzwarth, N. A. W. Physical Review B, Vol. 92, Issue 21 https://doi.org/10.1103/PhysRevB.92.214201	journal	December 2015
Deep Potential Molecular Dynamics: A Scalable Model with the Accuracy of Quantum Mechanics Zhang, Linfeng; Han, Jiequn; Wang, Han Physical Review Letters, Vol. 120, Issue 14 https://doi.org/10.1103/PhysRevLett.120.143001	journal	April 2018
First-Principles Prediction of Potentials and Space-Charge Layers in All-Solid-State Batteries Swift, Michael W.; Qi, Yue Physical Review Letters, Vol. 122, Issue 16 https://doi.org/10.1103/PhysRevLett.122.167701	journal	April 2019
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy Li, Yuzhang; Li, Yanbin; Pei, Allen Science, Vol. 358, Issue 6362 https://doi.org/10.1126/science.aam6014	journal	October 2017
Capturing the swelling of solid-electrolyte interphase in lithium metal batteries Zhang, Zewen; Li, Yuzhang; Xu, Rong Science, Vol. 375, Issue 6576 https://doi.org/10.1126/science.abi8703	journal	January 2022
Designing better electrolytes Meng, Y. Shirley; Srinivasan, Venkat; Xu, Kang Science, Vol. 378, Issue 6624 https://doi.org/10.1126/science.abq3750	journal	December 2022
The Surface Chemistry of Lithium Electrodes in Alkyl Carbonate Solutions Aurbach, Doron Journal of The Electrochemical Society, Vol. 141, Issue 1 https://doi.org/10.1149/1.2054718	journal	January 1994
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model Peled, E. Journal of The Electrochemical Society, Vol. 126, Issue 12 https://doi.org/10.1149/1.2128859	journal	January 1979
The absolute electrode potential: an explanatory note (Recommendations 1986) Trasatti, S. Pure and Applied Chemistry, Vol. 58, Issue 7 https://doi.org/10.1351/pac198658070955	journal	January 1986

Similar Records

Understanding the Role of Borohydride Doping in Electrochemical Stability of Argyrodite Li ₆PS₅Cl Solid‐State Electrolyte

Journal Article · 2025 · Advanced Materials · OSTI ID:3015583

Wang, Yixian; Raj, Vikalp; Yan, Qianqian; +12 more

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Journal Article · 2025 · Advanced Materials · OSTI ID:2497380

Wang, Yixian; Raj, Vikalp; Naik, Kaustubh G.; +13 more

The Importance of a Moving Boundary Approach for Modeling the SEI Layer Growth to Predict Capacity Fade

Journal Article · 2022 · Journal of the Electrochemical Society · OSTI ID:2325347

Uppaluri, Maitri; Shah, Krishna; Viswanathan, Vilayanur; +1 more

Related Subjects

25 ENERGY STORAGE

Title: Visualizing the SEI formation between lithium metal and solid-state electrolyte

Citation Formats

References (63)

Similar Records

Related Subjects