Investigation of Complex Intermediates in Solvent-Mediated Synthesis of Thiophosphate Solid-State Electrolytes

Delnick, Frank M.; Yang, Guang; Self, Ethan C.; Meyer III, Harry M.; Nanda, Jagjit

doi:10.1021/acs.jpcc.0c08761

Investigation of Complex Intermediates in Solvent-Mediated Synthesis of Thiophosphate Solid-State Electrolytes

Journal Article · Wed Dec 02 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c08761· OSTI ID:1764469

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Lithium thiophosphates represent a promising class of solid Li⁺ conductors for all-solid-state batteries. Scalable solvent-mediated synthesis routes for several Li–P–S ternary compounds have been reported, but little is known regarding the reaction mechanism of such pathways. This work demonstrates that solvent-mediated synthesis of lithium thiophosphate solid electrolytes from mixtures of Li₂S and P₂S₅ proceeds through a highly soluble P₂S₆^2– intermediate. This intermediate exhibits virtually the same Raman spectra in several solvents including acetonitrile, methyl acetate, ethyl acetate, ethyl propionate, dimethoxyethane, tetraethylene glycol dimethyl ether, and tetrahydrofuran. Additionally, based on this universal intermediate, a general reaction mechanism is proposed for the solvent-mediated synthesis of several lithium thiophosphates including (LiPS₃)_n, Li₂P₂S₆, Li₇P₃S₁₁, and Li₃PS₄.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1764469

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 50 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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