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Title: Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries

Abstract

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. Furthermore, this perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.

Authors:
 [1];  [1];  [2];  [3];  [4];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Illinois at Urbana-Champaign, Urbana, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1339571
Report Number(s):
SAND-2016-8614J
Journal ID: ISSN 2380-8195; 128280
Grant/Contract Number:
AC02-06CH11357; AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 1; Journal Issue: 3; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Cheng, Lei, Curtiss, Larry A., Zavadil, Kevin R., Gewirth, Andrew A., Shao, Yuyan, and Gallagher, Kevin G. Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries. United States: N. p., 2016. Web. doi:10.1021/acsenergylett.6b00194.
Cheng, Lei, Curtiss, Larry A., Zavadil, Kevin R., Gewirth, Andrew A., Shao, Yuyan, & Gallagher, Kevin G. Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries. United States. doi:10.1021/acsenergylett.6b00194.
Cheng, Lei, Curtiss, Larry A., Zavadil, Kevin R., Gewirth, Andrew A., Shao, Yuyan, and Gallagher, Kevin G. 2016. "Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries". United States. doi:10.1021/acsenergylett.6b00194. https://www.osti.gov/servlets/purl/1339571.
@article{osti_1339571,
title = {Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries},
author = {Cheng, Lei and Curtiss, Larry A. and Zavadil, Kevin R. and Gewirth, Andrew A. and Shao, Yuyan and Gallagher, Kevin G.},
abstractNote = {Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems that fundamentally decouple electrolyte volume from reaction mechanism. Furthermore, this perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.},
doi = {10.1021/acsenergylett.6b00194},
journal = {ACS Energy Letters},
number = 3,
volume = 1,
place = {United States},
year = 2016,
month = 7
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 5works
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  • Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systemsmore » that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less
  • Moving to lighter and less expensive battery chemistries compared to contemporary lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium–sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation–dissolution chemistry require large excesses of electrolyte to fully solubilize the polysulfide intermediates. Achieving reversible electrochemistry under lean electrolyte operation is the most promising path for Li/S to move beyond niche applications to potentially transformational performance. An emerging Li/S research area is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systems thatmore » fundamentally decouple electrolyte volume from sulfur and polysulfide reaction mechanism. Lastly, this Perspective presents an outlook for sparingly solvating electrolytes as a key path forward for long-lived, high energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less
  • 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 sparinglymore » 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.« less
    Cited by 5
  • 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 sparinglymore » 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.« less
  • 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 sparinglymore » 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. 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
    Cited by 5