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Title: Exploring the bottlenecks of anionic redox in Li-rich layered sulfides

Abstract

Anionic redox chemistry has emerged as a new paradigm to design higher-energy lithium ion-battery cathode materials such as Li-rich layered oxides. However, they suffer from voltage fade, large hysteresis and sluggish kinetics, which originate intriguingly from the anionic redox activity itself. To fundamentally understand these issues, we decided to act on the ligand by designing new Li-rich layered sulfides Li1.33 – 2y/3Ti0.67 – y/3FeyS2, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g-1 due to cumulated cationic (Fe2+/3+) and anionic (S2-/Sn-, n < 2) redox processes. Moreover, its negligible initial cycle irreversibility, mitigated voltage fade upon long cycling, low voltage hysteresis and fast kinetics compare positively with its Li-rich oxide analogues. Moving from the oxygen ligand to the sulfur ligand thus partially alleviates the practical bottlenecks affecting anionic redox, although it penalizes the redox potential and energy density. Overall, these sulfides provide chemical clues to improve the holistic performance of anionic redox electrodes, which may guide us to ultimately exploit the energy benefits of oxygen redox.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [7]; ORCiD logo [7]; ORCiD logo [4];  [1];  [8]; ORCiD logo [1]
  1. Collège de France, Paris (France); Sorbonne Univ., Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
  2. National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France); ALISTORE-European Research Inst. (France)
  3. National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France)
  4. Univ. of Illinois, Chicago, IL (United States)
  5. Collège de France, Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
  6. Collège de France, Paris (France)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Skolkovo Inst. of Science and Technology, Moscow (Russia). Center for Energy Science and Technology
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1594935
Grant/Contract Number:  
AC02-05CH11231; AC02- 06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 4; Journal Issue: 11; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., and Tarascon, Jean-Marie. Exploring the bottlenecks of anionic redox in Li-rich layered sulfides. United States: N. p., 2019. Web. doi:10.1038/s41560-019-0493-0.
Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., & Tarascon, Jean-Marie. Exploring the bottlenecks of anionic redox in Li-rich layered sulfides. United States. doi:https://doi.org/10.1038/s41560-019-0493-0
Saha, Sujoy, Assat, Gaurav, Sougrati, Moulay Tahar, Foix, Dominique, Li, Haifeng, Vergnet, Jean, Turi, Soma, Ha, Yang, Yang, Wanli, Cabana, Jordi, Rousse, Gwenaëlle, Abakumov, Artem M., and Tarascon, Jean-Marie. Thu . "Exploring the bottlenecks of anionic redox in Li-rich layered sulfides". United States. doi:https://doi.org/10.1038/s41560-019-0493-0. https://www.osti.gov/servlets/purl/1594935.
@article{osti_1594935,
title = {Exploring the bottlenecks of anionic redox in Li-rich layered sulfides},
author = {Saha, Sujoy and Assat, Gaurav and Sougrati, Moulay Tahar and Foix, Dominique and Li, Haifeng and Vergnet, Jean and Turi, Soma and Ha, Yang and Yang, Wanli and Cabana, Jordi and Rousse, Gwenaëlle and Abakumov, Artem M. and Tarascon, Jean-Marie},
abstractNote = {Anionic redox chemistry has emerged as a new paradigm to design higher-energy lithium ion-battery cathode materials such as Li-rich layered oxides. However, they suffer from voltage fade, large hysteresis and sluggish kinetics, which originate intriguingly from the anionic redox activity itself. To fundamentally understand these issues, we decided to act on the ligand by designing new Li-rich layered sulfides Li1.33 – 2y/3Ti0.67 – y/3FeyS2, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g-1 due to cumulated cationic (Fe2+/3+) and anionic (S2-/Sn-, n < 2) redox processes. Moreover, its negligible initial cycle irreversibility, mitigated voltage fade upon long cycling, low voltage hysteresis and fast kinetics compare positively with its Li-rich oxide analogues. Moving from the oxygen ligand to the sulfur ligand thus partially alleviates the practical bottlenecks affecting anionic redox, although it penalizes the redox potential and energy density. Overall, these sulfides provide chemical clues to improve the holistic performance of anionic redox electrodes, which may guide us to ultimately exploit the energy benefits of oxygen redox.},
doi = {10.1038/s41560-019-0493-0},
journal = {Nature Energy},
number = 11,
volume = 4,
place = {United States},
year = {2019},
month = {11}
}

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