Suppression of O-redox reactions by multivalent Cr in Li-excess Li2.4M0.8M0.8′O4 (M, M’ = Cr, Mn, and Ti) cathodes with layered and cation-disordered rock-salt structures

Motoyuki Hamaguchi; Hiroyoshi Momida; Ayuko Kitajou; Shigeto Okada; Tamio Oguchi

doi:10.1016/j.electacta.2020.136630

Suppression of O-redox reactions by multivalent Cr in Li-excess Li_2.4M_0.8M_0.8^′O₄ (M, M’ = Cr, Mn, and Ti) cathodes with layered and cation-disordered rock-salt structures

Motoyuki Hamaguchi, Hiroyoshi Momida, Ayuko Kitajou, Shigeto Okada, Tamio Oguchi

Department of Advanced Device Materials

Research output: Contribution to journal › Article › peer-review

Abstract

We study cathode properties of Li-excess Li_2.4M_0.8M_0.8^′O₄ (M, M’= Cr, Mn, and Ti) materials with layered and cation-disordered rock-salt structures by first-principles calculations. Results show that, as Li-removal amounts y increase in Li_2.4-yM_0.8M_0.8^′O₄, local structures at a certain amount of cation sites change from octahedral to tetrahedral coordinations with O especially at Cr sites. Calculated voltage–capacity curves are consistent with experimental results, and it is found that Cr-redox reactions predominate in whole y ranges for (M, M’) = (Cr, Mn) and (Cr, Ti), while Mn-redox and O-redox at low and high y regions, respectively, are dominated for (M, M’) = (Mn, Ti). In the cathode materials with Cr, both O-redox and O₂-release reactions are found to be suppressed by multivalent Cr.

Original language	English
Article number	136630
Journal	Electrochimica Acta
Volume	354
DOIs	https://doi.org/10.1016/j.electacta.2020.136630
Publication status	Published - Sep 10 2020

All Science Journal Classification (ASJC) codes

Chemical Engineering(all)
Electrochemistry

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Suppression of O-redox reactions by multivalent Cr in Li-excess Li_2.4M_0.8M_0.8^′O₄ (M, M’ = Cr, Mn, and Ti) cathodes with layered and cation-disordered rock-salt structures. / Hamaguchi, Motoyuki; Momida, Hiroyoshi; Kitajou, Ayuko; Okada, Shigeto; Oguchi, Tamio.

In: Electrochimica Acta, Vol. 354, 136630, 10.09.2020.

Research output: Contribution to journal › Article › peer-review

@article{6a28e3aa52aa4065b589da084753cd6c,

title = "Suppression of O-redox reactions by multivalent Cr in Li-excess Li2.4M0.8M0.8′O4 (M, M{\textquoteright} = Cr, Mn, and Ti) cathodes with layered and cation-disordered rock-salt structures",

abstract = "We study cathode properties of Li-excess Li2.4M0.8M0.8′O4 (M, M{\textquoteright}= Cr, Mn, and Ti) materials with layered and cation-disordered rock-salt structures by first-principles calculations. Results show that, as Li-removal amounts y increase in Li2.4-yM0.8M0.8′O4, local structures at a certain amount of cation sites change from octahedral to tetrahedral coordinations with O especially at Cr sites. Calculated voltage–capacity curves are consistent with experimental results, and it is found that Cr-redox reactions predominate in whole y ranges for (M, M{\textquoteright}) = (Cr, Mn) and (Cr, Ti), while Mn-redox and O-redox at low and high y regions, respectively, are dominated for (M, M{\textquoteright}) = (Mn, Ti). In the cathode materials with Cr, both O-redox and O2-release reactions are found to be suppressed by multivalent Cr.",

author = "Motoyuki Hamaguchi and Hiroyoshi Momida and Ayuko Kitajou and Shigeto Okada and Tamio Oguchi",

note = "Funding Information: This work was supported by “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials”, Element Strategy Initiative of MEXT , Grant Number JPMXP0112101003 , and JSPS KAKENHI Grant Number JP19H05816 . The computation in this work was partly carried out using the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo. ",

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T1 - Suppression of O-redox reactions by multivalent Cr in Li-excess Li2.4M0.8M0.8′O4 (M, M’ = Cr, Mn, and Ti) cathodes with layered and cation-disordered rock-salt structures

AU - Hamaguchi, Motoyuki

AU - Momida, Hiroyoshi

AU - Kitajou, Ayuko

AU - Okada, Shigeto

AU - Oguchi, Tamio

N1 - Funding Information: This work was supported by “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials”, Element Strategy Initiative of MEXT , Grant Number JPMXP0112101003 , and JSPS KAKENHI Grant Number JP19H05816 . The computation in this work was partly carried out using the facilities of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo.

PY - 2020/9/10

Y1 - 2020/9/10

N2 - We study cathode properties of Li-excess Li2.4M0.8M0.8′O4 (M, M’= Cr, Mn, and Ti) materials with layered and cation-disordered rock-salt structures by first-principles calculations. Results show that, as Li-removal amounts y increase in Li2.4-yM0.8M0.8′O4, local structures at a certain amount of cation sites change from octahedral to tetrahedral coordinations with O especially at Cr sites. Calculated voltage–capacity curves are consistent with experimental results, and it is found that Cr-redox reactions predominate in whole y ranges for (M, M’) = (Cr, Mn) and (Cr, Ti), while Mn-redox and O-redox at low and high y regions, respectively, are dominated for (M, M’) = (Mn, Ti). In the cathode materials with Cr, both O-redox and O2-release reactions are found to be suppressed by multivalent Cr.

AB - We study cathode properties of Li-excess Li2.4M0.8M0.8′O4 (M, M’= Cr, Mn, and Ti) materials with layered and cation-disordered rock-salt structures by first-principles calculations. Results show that, as Li-removal amounts y increase in Li2.4-yM0.8M0.8′O4, local structures at a certain amount of cation sites change from octahedral to tetrahedral coordinations with O especially at Cr sites. Calculated voltage–capacity curves are consistent with experimental results, and it is found that Cr-redox reactions predominate in whole y ranges for (M, M’) = (Cr, Mn) and (Cr, Ti), while Mn-redox and O-redox at low and high y regions, respectively, are dominated for (M, M’) = (Mn, Ti). In the cathode materials with Cr, both O-redox and O2-release reactions are found to be suppressed by multivalent Cr.

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