Access to Ru(IV)-Ru(V) and Ru(V)-Ru(VI) Redox in Layered Li7RuO6via Intercalation Reactions

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

doi:10.1021/acs.chemmater.2c00043

Access to Ru(IV)-Ru(V) and Ru(V)-Ru(VI) Redox in Layered Li₇RuO₆via Intercalation Reactions

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

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Abstract

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 Li₇RuO₆is capable of highly reversible lithiation to Li₈RuO₆through the Ru(V)/Ru(IV) redox couple. Li₇RuO₆can 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.

Original language	English
Pages (from-to)	3724-3735
Number of pages	12
Journal	Chemistry of Materials
Volume	34
Issue number	8
DOIs	https://doi.org/10.1021/acs.chemmater.2c00043
State	Published - Apr 26 2022

Funding

This material is based upon work primarily supported by the National Science Foundation under Grant No. DMR-1809372. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Neutron diffraction data were collected at the POWGEN beamline at the Spallation Neutron Source, Oak Ridge National Laboratory, which was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U. S. Department of Energy.

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10.1021/acs.chemmater.2c00043

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title = "Access to Ru(IV)-Ru(V) and Ru(V)-Ru(VI) Redox in Layered Li7RuO6via Intercalation Reactions",

abstract = "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 Li7RuO6is capable of highly reversible lithiation to Li8RuO6through the Ru(V)/Ru(IV) redox couple. Li7RuO6can 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.",

author = "Haifeng Li and Beata Taudul and Alexander, {Grant C.B.} and Jue Liu and Freeland, {John W.} and Doublet, {Marie Liesse} and Jordi Cabana",

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T1 - Access to Ru(IV)-Ru(V) and Ru(V)-Ru(VI) Redox in Layered Li7RuO6via Intercalation Reactions

AU - Li, Haifeng

AU - Taudul, Beata

AU - Alexander, Grant C.B.

AU - Liu, Jue

AU - Freeland, John W.

AU - Doublet, Marie Liesse

AU - Cabana, Jordi

PY - 2022/4/26

Y1 - 2022/4/26

N2 - 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 Li7RuO6is capable of highly reversible lithiation to Li8RuO6through the Ru(V)/Ru(IV) redox couple. Li7RuO6can 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.

AB - 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 Li7RuO6is capable of highly reversible lithiation to Li8RuO6through the Ru(V)/Ru(IV) redox couple. Li7RuO6can 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.

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