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

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

doi:10.1038/s41560-019-0493-0

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

Journal Article · Wed Nov 13 23:00:00 EST 2019 · Nature Energy

DOI:https://doi.org/10.1038/s41560-019-0493-0· OSTI ID:1594935

Saha, Sujoy ^[1]; ^[1]; ^[2]; Foix, Dominique ^[3]; Li, Haifeng ^[4]; ^[5]; Turi, Soma ^[6]; ^[7]; ^[7]; ^[4]; Rousse, Gwenaëlle ^[1]; Abakumov, Artem M. ^[8]; ^[1]

Collège de France, Paris (France); Sorbonne Univ., Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France); ALISTORE-European Research Inst. (France)
National Centre for Scientific Research-Mixed Organizations (CNRS-UMR), Paris (France)
Univ. of Illinois, Chicago, IL (United States)
Collège de France, Paris (France); Centre National de la Recherche Scientifique (CNRS), Paris (France)
Collège de France, Paris (France)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Skolkovo Inst. of Science and Technology, Moscow (Russia). Center for Energy Science and Technology

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 Li_{1.33 – 2y/3}Ti_{0.67 – y/3}FeyS₂, among which the y = 0.3 member shows sustained reversible capacities of ~245 mAh g^-1 due to cumulated cationic (Fe²⁺/³⁺) and anionic (S^2-/S^n-, 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1594935

Alternate ID(s):: OSTI ID: 1631833

Journal Information:: Nature Energy, Journal Name: Nature Energy Journal Issue: 11 Vol. 4; ISSN 2058-7546

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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