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Title: Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs

Abstract

Cathodes based on layered LiMO2 are the limiting components in the path toward Li-ion batteries with energy densities suitable for electric vehicles. Introducing an over-stoichiometry of Li increases storage capacity beyond a conventional mechanism of formal transition metal redox. However, the role and fate of the oxide ligands in such intriguing additional capacity remain unclear. This reactivity was predicted in Li3RuO4, making it a valuable model system. For this study, a comprehensive analysis of the redox activity of both Ru and O under different electrochemical conditions was carried out, and the effect of Li/Ru ordering was evaluated. Li3RuO4 displays highly reversible Li intercalation to Li4RuO4 below 2.5 V vs Li+/Li0, with conventional reactivity through the formal Ru5+-Ru4+ couple. In turn, it can also undergo anodic Li extraction at 3.9 V, which involves O states to a much greater extent than Ru. This reaction competes with side processes such as electrolyte decomposition and, to a much lesser extent, oxygen loss. Although the associated capacity is reversible, reintercalation unlocks a different, conventional pathway also involving the formal Ru5+-Ru4+ couple despite operating above 2.5 V, leading to chemical hysteresis. This new pathway is both chemically and electrochemically reversible in subsequent cycles. This workmore » exemplifies both the challenge of stabilizing highly depleted O states, even with 4d metals, and the ability of solids to access the same redox couple at two very different potential windows depending on the underlying structural changes. It highlights the importance of properly defining the covalency of oxides when defining charge compensation in view of the design of materials with high capacity for Li storage.« less

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Illinois, Chicago, IL (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1660429
Grant/Contract Number:  
AC02-06CH11357; DMR-1809372
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 18; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Haifeng, Ramakrishnan, Srinivasan, Freeland, John W., McCloskey, Bryan D., and Cabana, Jordi. Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs. United States: N. p., 2020. Web. doi:10.1021/jacs.9b12438.
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Li, Haifeng, Ramakrishnan, Srinivasan, Freeland, John W., McCloskey, Bryan D., & Cabana, Jordi. Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs. United States. https://doi.org/10.1021/jacs.9b12438
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Li, Haifeng, Ramakrishnan, Srinivasan, Freeland, John W., McCloskey, Bryan D., and Cabana, Jordi. Thu . "Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs". United States. https://doi.org/10.1021/jacs.9b12438. https://www.osti.gov/servlets/purl/1660429.
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@article{osti_1660429,
title = {Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs},
author = {Li, Haifeng and Ramakrishnan, Srinivasan and Freeland, John W. and McCloskey, Bryan D. and Cabana, Jordi},
abstractNote = {Cathodes based on layered LiMO2 are the limiting components in the path toward Li-ion batteries with energy densities suitable for electric vehicles. Introducing an over-stoichiometry of Li increases storage capacity beyond a conventional mechanism of formal transition metal redox. However, the role and fate of the oxide ligands in such intriguing additional capacity remain unclear. This reactivity was predicted in Li3RuO4, making it a valuable model system. For this study, a comprehensive analysis of the redox activity of both Ru and O under different electrochemical conditions was carried out, and the effect of Li/Ru ordering was evaluated. Li3RuO4 displays highly reversible Li intercalation to Li4RuO4 below 2.5 V vs Li+/Li0, with conventional reactivity through the formal Ru5+-Ru4+ couple. In turn, it can also undergo anodic Li extraction at 3.9 V, which involves O states to a much greater extent than Ru. This reaction competes with side processes such as electrolyte decomposition and, to a much lesser extent, oxygen loss. Although the associated capacity is reversible, reintercalation unlocks a different, conventional pathway also involving the formal Ru5+-Ru4+ couple despite operating above 2.5 V, leading to chemical hysteresis. This new pathway is both chemically and electrochemically reversible in subsequent cycles. This work exemplifies both the challenge of stabilizing highly depleted O states, even with 4d metals, and the ability of solids to access the same redox couple at two very different potential windows depending on the underlying structural changes. It highlights the importance of properly defining the covalency of oxides when defining charge compensation in view of the design of materials with high capacity for Li storage.},
doi = {10.1021/jacs.9b12438},
journal = {Journal of the American Chemical Society},
number = 18,
volume = 142,
place = {United States},
year = {Thu Apr 09 00:00:00 EDT 2020},
month = {Thu Apr 09 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/jacs.9b12438
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