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Mechanistic insights into superionic thioarsenate argyrodite solid electrolytes via machine learning interatomic potentials

Journal Article · · Journal of Materials Chemistry A
DOI:https://doi.org/10.1039/d5ta05538e· OSTI ID:2998154
 [1];  [2];  [2];  [3];  [4];  [5]
  1. Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of); Korea Univ., Seoul, (Korea, Republic of)
  2. Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of)
  3. Korea Univ., Seoul, (Korea, Republic of)
  4. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Laboratory for Energy Applications for the Future (LEAF)
  5. Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of); Korea University of Science and Technology, Seoul, (Korea, Republic of)
+ Show Author Affiliations

The lithium argyrodite sulfide solid electrolyte Li6PS5Cl has attracted considerable interest for all-solid-state batteries owing to its high ionic conductivity, which can be further enhanced through ionic substitution. Although a variety of substitutions have been investigated, thioarsenate argyrodites remain comparatively underexplored. Here, we systematically investigate the phase stability and Li-ion conduction mechanisms in superionic Br-incorporated thioarsenate argyrodites using first-principles calculations and molecular dynamics simulations based on machine learning interatomic potentials (MLIPs). Systematic variation of S/Br site inversion reveals that an optimal degree of anion disorder significantly enhances inter-cage connectivity and facilitates long-range Li-ion diffusion. Configurational entropy serves as an effective quantitative descriptor of anion disorder, exhibiting a strong correlation with ionic conductivity. While greater anion disorder induced by site inversion and higher Br content enhances ionic conductivity up to 50 mS cm−1, it simultaneously reduces structural stability. This trade-off results in an optimal window in which a moderate level of disorder yields conductivities exceeding 20 mS cm−1 while maintaining synthetic feasibility. In conclusion, this work highlights the reliability and efficiency of MLIPs for elucidating ion-transport mechanisms and accelerating the design of novel superionic argyrodites.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); Korea Institute of Science and Technology; National Research Foundation of Korea (NRF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
2998154
Report Number(s):
LLNL--JRNL-2006170
Journal Information:
Journal of Materials Chemistry A, Journal Name: Journal of Materials Chemistry A Journal Issue: 39 Vol. 13; ISSN 2050-7496; ISSN 2050-7488
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United States
Language:
English

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