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An Exploration of Sulfur Redox in Lithium Battery Cathodes

Zak, Joshua J. and Kim, Seong Shik and Laskowski, Forrest A. L. and See, Kimberly A. (2022) An Exploration of Sulfur Redox in Lithium Battery Cathodes. Journal of the American Chemical Society, 144 (23). pp. 10119-10132. ISSN 0002-7863. doi:10.1021/jacs.2c02668. https://resolver.caltech.edu/CaltechAUTHORS:20220606-736139000

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Abstract

Secondary Li-ion batteries have enabled a world of portable electronics and electrification of personal and commercial transportation. However, the charge storage capacity of conventional intercalation cathodes is reaching the theoretical limit set by the stoichiometry of Li in the fully lithiated structure. Increasing the Li:transition metal ratio and consequently involving structural anions in the charge compensation, a mechanism termed anion redox, is a viable method to improve storage capacities. Although anion redox has recently become the front-runner as a next-generation storage mechanism, the concept has been around for quite some time. In this perspective, we explore the contribution of anions in charge compensation mechanisms ranging from intercalation to conversion and the hybrid mechanisms between. We focus our attention on the redox of S because the voltage required to reach S redox lies within the electrolyte stability window, which removes the convoluting factors caused by the side reactions that plague the oxides. We highlight examples of S redox in cathode materials exhibiting varying degrees of anion involvement with a particular focus on the structural effects. We call attention to those with intermediate anion contribution to redox and the hybrid intercalation- and conversion-type structural mechanism at play that takes advantage of the positives of both mechanistic types to increase storage capacity while maintaining good reversibility. The hybrid mechanisms often invoke the formation of persulfides, and so a survey of binary and ternary materials containing persulfide moieties is presented to provide context for materials that show thermodynamically stable persulfide moieties.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.2c02668DOIArticle
ORCID:
AuthorORCID
Zak, Joshua J.0000-0003-3793-7254
Kim, Seong Shik0000-0003-2604-6392
Laskowski, Forrest A. L.0000-0001-8909-483X
See, Kimberly A.0000-0002-0133-9693
Additional Information:© 2022 American Chemical Society. Received: March 10, 2022; Published: June 2, 2022. This work was supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), and Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0019381. J.J.Z. acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1745301. F.A.L.L. acknowledges the support of the Arnold and Mabel Beckman Foundation via a 2020 Arnold O. Beckman Postdoctoral Fellowship in Chemical Sciences. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0019381
NSF Graduate Research FellowshipDGE-1745301
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Anions, Chemical structure, Materials, Oxidation, Redox reactions
Issue or Number:23
DOI:10.1021/jacs.2c02668
Record Number:CaltechAUTHORS:20220606-736139000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220606-736139000
Official Citation:An Exploration of Sulfur Redox in Lithium Battery Cathodes. Joshua J. Zak, Seong Shik Kim, Forrest A. L. Laskowski, and Kimberly A. See. Journal of the American Chemical Society 2022 144 (23), 10119-10132; DOI: 10.1021/jacs.2c02668
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:115029
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:07 Jun 2022 16:34
Last Modified:27 Jun 2022 15:51

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