All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators
Abstract
We report redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li2S) oxidation in solid polymer electrolytes. Accordingly, Li2S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh gs-1. Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li2S cathodes with RMs facilitated Li2S oxidation. In contrast, for bare Li2S cathodes, the solid-solid Li2S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to ~4 V) and low sulfur utilization. The Li2S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work revealsmore »
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1];
[2]
- Stanford University, CA (United States)
- Stanford University, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
- OSTI Identifier:
- 1874795
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 43; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Gao, Xin, Zheng, Xueli, Tsao, Yuchi, Zhang, Pu, Xiao, Xin, Ye, Yusheng, Li, Jun, Yang, Yufei, Xu, Rong, Bao, Zhenan, and Cui, Yi. All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c07754.
Gao, Xin, Zheng, Xueli, Tsao, Yuchi, Zhang, Pu, Xiao, Xin, Ye, Yusheng, Li, Jun, Yang, Yufei, Xu, Rong, Bao, Zhenan, & Cui, Yi. All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators. United States. https://doi.org/10.1021/jacs.1c07754
Gao, Xin, Zheng, Xueli, Tsao, Yuchi, Zhang, Pu, Xiao, Xin, Ye, Yusheng, Li, Jun, Yang, Yufei, Xu, Rong, Bao, Zhenan, and Cui, Yi. Fri .
"All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators". United States. https://doi.org/10.1021/jacs.1c07754. https://www.osti.gov/servlets/purl/1874795.
@article{osti_1874795,
title = {All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators},
author = {Gao, Xin and Zheng, Xueli and Tsao, Yuchi and Zhang, Pu and Xiao, Xin and Ye, Yusheng and Li, Jun and Yang, Yufei and Xu, Rong and Bao, Zhenan and Cui, Yi},
abstractNote = {We report redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li2S) oxidation in solid polymer electrolytes. Accordingly, Li2S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh gs-1. Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li2S cathodes with RMs facilitated Li2S oxidation. In contrast, for bare Li2S cathodes, the solid-solid Li2S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to ~4 V) and low sulfur utilization. The Li2S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work reveals the evolution of sulfur species in ASSLSBs and realizes the fast Li-S reaction kinetics by designing an effective sulfur speciation pathway},
doi = {10.1021/jacs.1c07754},
journal = {Journal of the American Chemical Society},
number = 43,
volume = 143,
place = {United States},
year = {Fri Oct 22 00:00:00 EDT 2021},
month = {Fri Oct 22 00:00:00 EDT 2021}
}
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