Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries

Gil-González, Eva; Ye, Luhan; Wang, Yichao; Shadike, Zulipiya; Xu, Zhenming; Hu, Enyuan; Li, Xin

doi:10.1016/j.ensm.2021.12.008

Title: Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries

Journal Article · 09 December 2022 · Energy Storage Materials

DOI: https://doi.org/10.1016/j.ensm.2021.12.008 · OSTI ID:1839215

Gil-González, Eva ^[1]; Ye, Luhan ^[1]; Wang, Yichao ^[1]; Shadike, Zulipiya ^[2]; Xu, Zhenming ^[1];

^[2]; Li, Xin ^[1]

Harvard Univ., Cambridge, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.

All-solid-state battery is considered as one of the most promising competitors to Li ion batteries. Two widely known performance metrics for solid electrolytes, among others, are ionic conductivity and stability. In this study, it is found that both can be improved by the synergistic effects of chlorine substitution in sulfide-based solid electrolytes. Particularly, instabilities arising from both bulk decompositions and interfacial reactions to electrodes can be better inhibited in the chlorine substituted sulfide solid electrolytes through the increased susceptibility to the mechanical constriction induced enhancement of voltage stability. As a result, the stability window of some chlorine-rich Li-argyrodites can be systematically higher than some other chlorine-deficient or chlorine-free electrolytes, especially under the implementation of the mechanical constriction battery assembly and test conditions. Thus, a solid-state battery system of 4 V to 5 V-class cathodes paired with lithium metal anode is demonstrated using these chlorine-rich Li-argyrodites without additional coatings. Furthermore, since Cl composition modulates the stability and instability of Li-argyrodite at low voltages, it allows us to design a multilayer configuration with a hierarchy of Li metal stabilities to demonstrate the stable cycling at relatively high current densities for solid-state batteries. It is found that a moderate Cl composition in the electrolyte is the best to inhibit Li dendrite penetration as the central electrolyte layer, emphasizing a slightly increased “instability” as the hidden performance metric of relevance here, in addition to the two well-known metrics of stability and ionic conductivity. The understanding of the chlorine substitution effect in sulfide electrolytes provides an important design principle for all-solid-state batteries.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704; AC02-06CH11357

OSTI ID:: 1839215

Report Number(s):: BNL-222585-2022-JAAM

Journal Information:: Energy Storage Materials, Vol. 45; ISSN 2405-8297

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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