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Title: Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries

Abstract

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur atmore » practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

Authors:
; ORCiD logo; ; ; ORCiD logo; ; ; ORCiD logo;
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1358466
Alternate Identifier(s):
OSTI ID: 1368568; OSTI ID: 1372260
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Lee, Chang-Wook, Pang, Quan, Ha, Seungbum, Cheng, Lei, Han, Sang-Don, Zavadil, Kevin R., Gallagher, Kevin G., Nazar, Linda F., and Balasubramanian, Mahalingam. Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries. United States: N. p., 2017. Web. doi:10.1021/acscentsci.7b00123.
Lee, Chang-Wook, Pang, Quan, Ha, Seungbum, Cheng, Lei, Han, Sang-Don, Zavadil, Kevin R., Gallagher, Kevin G., Nazar, Linda F., & Balasubramanian, Mahalingam. Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries. United States. https://doi.org/10.1021/acscentsci.7b00123
Lee, Chang-Wook, Pang, Quan, Ha, Seungbum, Cheng, Lei, Han, Sang-Don, Zavadil, Kevin R., Gallagher, Kevin G., Nazar, Linda F., and Balasubramanian, Mahalingam. Thu . "Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries". United States. https://doi.org/10.1021/acscentsci.7b00123.
@article{osti_1358466,
title = {Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries},
author = {Lee, Chang-Wook and Pang, Quan and Ha, Seungbum and Cheng, Lei and Han, Sang-Don and Zavadil, Kevin R. and Gallagher, Kevin G. and Nazar, Linda F. and Balasubramanian, Mahalingam},
abstractNote = {The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.},
doi = {10.1021/acscentsci.7b00123},
journal = {ACS Central Science},
number = ,
volume = ,
place = {United States},
year = {Thu May 25 00:00:00 EDT 2017},
month = {Thu May 25 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscentsci.7b00123

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