title: Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.
abstract: Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1based on solid-state redox reaction of oxide ions.
authors.affiliation: Department of Green and Sustainable Chemistry, Tokyo Denki University, 5Senju Asahi-Cho, Adachi, Tokyo 120-8551, Japan.
authors.forename: Naoaki
authors.identifier: 0000-0002-9404-5693
authors.initials: N
authors.lastname: Yabuuchi
authors.affiliation: Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan.|Japan Science and Technology Agency (JST), PRESTO, 4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan.
authors.forename: Masanobu
authors.initials: M
authors.lastname: Nakayama
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan.
authors.forename: Mitsue
authors.initials: M
authors.lastname: Takeuchi
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan.
authors.forename: Shinichi
authors.initials: S
authors.lastname: Komaba
authors.affiliation: Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan.
authors.forename: Yu
authors.initials: Y
authors.lastname: Hashimoto
authors.affiliation: Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Mukai
authors.affiliation: Frontier Research Institute for Materials Science, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan.
authors.forename: Hiromasa
authors.initials: H
authors.lastname: Shiiba
authors.affiliation: Department of Green and Sustainable Chemistry, Tokyo Denki University, 5Senju Asahi-Cho, Adachi, Tokyo 120-8551, Japan.
authors.forename: Kei
authors.initials: K
authors.lastname: Sato
authors.affiliation: Department of Green and Sustainable Chemistry, Tokyo Denki University, 5Senju Asahi-Cho, Adachi, Tokyo 120-8551, Japan.
authors.forename: Yuki
authors.initials: Y
authors.lastname: Kobayashi
authors.affiliation: Bio-engineering Lab., Riken, 2-1 Hirosawa, Wako, Satimata 351-0198, Japan.
authors.forename: Aiko
authors.initials: A
authors.lastname: Nakao
authors.affiliation: Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.|Department of Materials Structure Science, Sokendai (The Graduate University for Advanced Studies), 203-1 Shirakata, Tokai, Ibaraki 319-1106, Japan.
authors.forename: Masao
authors.initials: M
authors.lastname: Yonemura
authors.affiliation: SR Center, Ritsumeikan University, 1-1-1 Noji-Higashi, Kusatsu, Shiga 525-8577, Japan.
authors.forename: Keisuke
authors.initials: K
authors.lastname: Yamanaka
authors.affiliation: SR Center, Ritsumeikan University, 1-1-1 Noji-Higashi, Kusatsu, Shiga 525-8577, Japan.
authors.forename: Kei
authors.initials: K
authors.lastname: Mitsuhara
authors.affiliation: SR Center, Ritsumeikan University, 1-1-1 Noji-Higashi, Kusatsu, Shiga 525-8577, Japan.
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Ohta