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

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/d3ee03536k· OSTI ID:2497723
 [1];  [1];  [2];  [3];  [1];  [1];  [4];  [3];  [1];  [4];  [3];  [1];  [1]
  1. Xiamen University (China)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
  3. Karlsruhe Inst. of Technology (KIT) (Germany)
  4. Chinese Academy of Sciences (CAS), Ningbo (China). Ningbo Institute of Materials Technology and Engineering
+ Show Author Affiliations
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.
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

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