Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of Ba5Ru2O11 in Aqueous and Organic Solvents

Grimaud, Alexis; Iadecola, Antonella; Batuk, Dmitry; Saubanère, Matthieu; Abakumov, Artem M.; Freeland, John W.; Cabana, Jordi; Li, Haifeng; Doublet, Marie-Liesse; Rousse, Gwenaëlle; Tarascon, Jean-Marie

doi:10.1021/acs.chemmater.8b01372

Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of Ba₅Ru₂O₁₁ in Aqueous and Organic Solvents

Journal Article · Mon May 21 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b01372· OSTI ID:1467567

^[1]; Iadecola, Antonella ^[2]; ^[3]; ^[4]; ^[5]; Freeland, John W. ^[6]; ^[7]; Li, Haifeng ^[8]; Doublet, Marie-Liesse ^[4]; ^[9]; Tarascon, Jean-Marie ^[9]

Collège de France, Paris (France). Chimie du Solide et de l’Energie; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France)
Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France)
Collège de France, Paris (France). Chimie du Solide et de l’Energie; Univ. of Antwerp, Antwerp (Belgium)
Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France); Univ. Montpellier II (France). Inst. Charles Gerhardt
Univ. of Antwerp, Antwerp (Belgium)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
Collège de France, Paris (France). Chimie du Solide et de l’Energie; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens (France); Sorbonne Univ., Paris (France)

The finding that triggering the redox activity of oxygen ions within the lattice of transition metal oxides can boost the performances of materials used in energy storage and conversion devices such as Li-ion batteries or oxygen evolution electrocatalysts has recently spurred intensive and innovative research in the field of energy. While experimental and theoretical efforts have been critical in understanding the role of oxygen nonbonding states in the redox activity of oxygen ions, a clear picture of the redox chemistry of the oxygen species formed upon this oxidation process is still missing. This can be, in part, explained by the complexity in stabilizing and studying these species once electrochemically formed. Here in this work, we alleviate this difficulty by studying the phase Ba₅Ru₂O₁₁, which contains peroxide O₂^2- groups, as oxygen evolution reaction electrocatalyst and Li-ion battery material. Combining physical characterization and electrochemical measurements, we demonstrate that peroxide groups can easily be oxidized at relatively low potential, leading to the formation of gaseous dioxygen and to the instability of the oxide. Furthermore, we demonstrate that, owing to the stabilization at high energy of peroxide, the high-lying energy of the empty sigma* antibonding O-O states limits the reversibility of the electrochemical reactions when the O₂^2-/O^2- redox couple is used as redox center for Li-ion battery materials or as OER redox active sites. Overall, this work suggests that the formation of true peroxide O₂^2- states are detrimental for transition metal oxides used as OER catalysts and Li-ion battery materials. Rather, oxygen species with O-O bond order lower than 1 would be preferred for these applications.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: European Research Council (ERC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1467567

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 30; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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