Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions

Li, Haifeng; Taudul, Beata; Alexander, Grant C. B.; Liu, Jue; Freeland, John W.; Doublet, Marie-Liesse; Cabana, Jordi

doi:10.1021/acs.chemmater.2c00043

Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li₇RuO₆ via Intercalation Reactions

Journal Article · Fri Apr 15 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c00043· OSTI ID:1901709

Li, Haifeng ^[1]; Taudul, Beata ^[2]; Alexander, Grant C. B. ^[1]; ^[3]; Freeland, John W. ^[4]; ^[2]; ^[1]

Univ. of Illinois, Chicago, IL (United States)
Université Montpellier (France); Centre National de la Recherche Scientifique (CNRS) (France); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)

The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li₇RuO₆. Coupling structural and spectroscopic analysis with computational simulations, we show that Li₇RuO₆ is capable of highly reversible lithiation to Li₈RuO₆ through the Ru(V)/Ru(IV) redox couple. Further, Li₇RuO₆ can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1901709

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 8 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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