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

Abstract

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 themore » 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.« less

Authors:
 [1];  [1];  [1];  [2];  [1]; ORCiD logo [2];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)
OSTI Identifier:
1839215
Report Number(s):
BNL-222585-2022-JAAM
Journal ID: ISSN 2405-8297
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Energy Storage Materials
Additional Journal Information:
Journal Volume: 45; Journal ID: ISSN 2405-8297
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium battery; solid state electrolyte

Citation Formats

Gil-González, Eva, Ye, Luhan, Wang, Yichao, Shadike, Zulipiya, Xu, Zhenming, Hu, Enyuan, and Li, Xin. Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries. United States: N. p., 2022. Web. doi:10.1016/j.ensm.2021.12.008.
Gil-González, Eva, Ye, Luhan, Wang, Yichao, Shadike, Zulipiya, Xu, Zhenming, Hu, Enyuan, & Li, Xin. Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries. United States. https://doi.org/10.1016/j.ensm.2021.12.008
Gil-González, Eva, Ye, Luhan, Wang, Yichao, Shadike, Zulipiya, Xu, Zhenming, Hu, Enyuan, and Li, Xin. Fri . "Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries". United States. https://doi.org/10.1016/j.ensm.2021.12.008.
@article{osti_1839215,
title = {Synergistic effects of chlorine substitution in sulfide electrolyte solid state batteries},
author = {Gil-González, Eva and Ye, Luhan and Wang, Yichao and Shadike, Zulipiya and Xu, Zhenming and Hu, Enyuan and Li, Xin},
abstractNote = {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.},
doi = {10.1016/j.ensm.2021.12.008},
journal = {Energy Storage Materials},
number = ,
volume = 45,
place = {United States},
year = {2022},
month = {12}
}

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