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Title: Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte

Journal Article · · ACS Energy Letters
 [1];  [1];  [1]; ORCiD logo [2];  [3];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
  1. Univ. of California San Diego, La Jolla, CA (United States). Dept. of NanoEngineering
  2. Univ. of California San Diego, La Jolla, CA (United States). Dept. of NanoEngineering; Univ. of California San Diego, La Jolla, CA (United States). Sustainable Power & Energy Center (SPEC)
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Science Directorate
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Sulfide-based solid electrolytes are promising candidates for all solid-state batteries (ASSBs) due to their high ionic conductivity and ease of processability. However, their narrow electrochemical stability window causes undesirable electrolyte decomposition. Existing literature on Li-ion ASSBs report an irreversible nature of such decompositions, while Li–S ASSBs show evidence of some reversibility. Here, we explain these observations by investigating the redox mechanism of argyrodite Li6PS5Cl at various chemical potentials. We found that Li–In | Li6PS5Cl | Li6PS5Cl–C half-cells can be cycled reversibly, delivering capacities of 965 mAh g–1 for the electrolyte itself. During charging, Li6PS5Cl forms oxidized products of sulfur (S) and phosphorus pentasulfide (P2S5), while during discharge, these products are first reduced to a Li3PS4 intermediate before forming lithium sulfide (Li2S) and lithium phosphide (Li3P). Lastly, we quantified the relative contributions of the products toward cell impedance and proposed a strategy to reduce electrolyte decomposition and increase cell Coulombic efficiency.

Research Organization:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1573940
Report Number(s):
LLNL-JRNL-786041; 981644
Journal Information:
ACS Energy Letters, Vol. 4, Issue 10; ISSN 2380-8195
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 165 works
Citation information provided by
Web of Science

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Stack Pressure Considerations for Room‐Temperature All‐Solid‐State Lithium Metal Batteries journal November 2019
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Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte journal October 2015

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