TY - JOUR
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.
Publisher Copyright:
© 2020 Elsevier Ltd
Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.
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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U2 - 10.1016/j.electacta.2020.136630
DO - 10.1016/j.electacta.2020.136630
M3 - Article
AN - SCOPUS:85087883915
VL - 354
JO - Electrochimica Acta
JF - Electrochimica Acta
SN - 0013-4686
M1 - 136630
ER -