Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Arnold, William; Shreyas, Varun; Li, Yang; Koralalage, Milinda Kalutara; Jasinski, Jacek B.; Thapa, Arjun; Sumanasekera, Gamini; Ngo, Anh T.; Narayanan, Badri; Wang, Hui

doi:10.1021/acsami.1c24468

Title: Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Journal Article · 23 February 2022 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.1c24468 · OSTI ID:1867866

Arnold, William ^[1]; Shreyas, Varun ^[1];

^[1]; Koralalage, Milinda Kalutara ^[1];

^[1]; Thapa, Arjun ^[1]; Sumanasekera, Gamini ^[1]; Ngo, Anh T. ^[2]; Narayanan, Badri ^[1];

^[1]

Univ. of Louisville, KY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the f irst time, we report F-doped Li_5+yPS₅F_y argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li₆PS₅F_0.5C_l0.5 exhibits the highest Li-ion conductivity of 3.5 x 10^-4 S cm^-1 at room temperature (RT). Furthermore, Li symmetric cells using Li⁶PS₅F_0.5Cl_0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li₆PS₅F_0.5C_l0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li₃P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: AC02-06CH11357; EE0008866

OSTI ID:: 1867866

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 9 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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