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Title: Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System
Authors: Fukuma, Ryutaro
Harada, Maho
Zhao, Wenwen
Sawamura, Miho
Noda, Yusuke
Nakayama, Masanobu
Goto, Masato
Kan, Daisuke
Shimakawa, Yuichi
Yonemura, Masao
Ikeda, Naohiro
Watanuki, Ryuta
Andersen, Henrik L.
D’Angelo, Anita M.
Sharma, Neeraj
Park, Jiwon
Byon, Hye Ryung
Fukuyama, Sayuri
Han, Zhenji
Fukumitsu, Hitoshi
Schulz-Dobrick, Martin
Yamanaka, Keisuke
Yamagishi, Hirona
Ohta, Toshiaki
Yabuuchi, Naoaki
Author's alias: 福間, 隆太朗
原田, 真帆
趙, 文文
澤村, 美穂
野田, 祐輔
中山, 将伸
後藤, 真人
菅, 大介
島川, 祐一
米村, 雅雄
池田, 直宏
綿貫, 竜太
福山, 小百合
韓, 貞姫
福満, 仁志
山中, 恵介
山岸, 弘奈
太田, 俊明
藪内, 直明
Keywords: Chemical structure
Redox reactions
Transition metals
Issue Date: 22-Jun-2022
Publisher: American Chemical Society (ACS)
Journal title: ACS Central Science
Volume: 8
Issue: 6
Start page: 775
End page: 794
Abstract: Dependence on lithium-ion batteries for automobile applications is rapidly increasing. The emerging use of anionic redox can boost the energy density of batteries, but the fundamental origin of anionic redox is still under debate. Moreover, to realize anionic redox, many reported electrode materials rely on manganese ions through π-type interactions with oxygen. Here, through a systematic experimental and theoretical study on a binary system of Li₃NbO₄–NiO, we demonstrate for the first time the unexpectedly large contribution of oxygen to charge compensation for electrochemical oxidation in Ni-based materials. In general, for Ni-based materials, e.g., LiNiO₂, charge compensation is achieved mainly by Ni oxidation, with a lower contribution from oxygen. In contrast, for Li₃NbO₄–NiO, oxygen-based charge compensation is triggered by structural disordering and σ-type interactions with nickel ions, which are associated with a unique environment for oxygen, i.e., a linear Ni–O–Ni configuration in the disordered system. Reversible anionic redox with a small hysteretic behavior was achieved for LiNi₂/₃Nb₁/₃O₂ with a cation-disordered Li/Ni arrangement. Further Li enrichment in the structure destabilizes anionic redox and leads to irreversible oxygen loss due to the disappearance of the linear Ni–O–Ni configuration and the formation of unstable Ni ions with high oxidation states. On the basis of these results, we discuss the possibility of using σ-type interactions for anionic redox to design advanced electrode materials for high-energy lithium-ion batteries.
Description: 酸素が反応に寄与するニッケル系電池材料 高エネルギー密度リチウム電池実現に期待 --新規不規則岩塩型ニッケル系材料開発と次世代蓄電池への応用--. 京都大学プレスリリース. 2022-05-24.
Rights: © 2022 The Authors. Published by American Chemical Society
This article is licensed under the Creative Commons Attribution 4.0 International License.
DOI(Published Version): 10.1021/acscentsci.2c00238
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