Kinetic square scheme in oxygen-redox battery electrodes

Kosuke Kawai; Xiang Mei Shi; Norio Takenaka; Jeonguk Jang; Benoit Mortemard de Boisse; Akihisa Tsuchimoto; Daisuke Asakura; Jun Kikkawa; Masanobu Nakayama; Masashi Okubo; Atsuo Yamada

doi:10.1039/d1ee03503g

Kinetic square scheme in oxygen-redox battery electrodes

Kosuke Kawai, Xiang Mei Shi, Norio Takenaka, Jeonguk Jang, Benoit Mortemard de Boisse, Akihisa Tsuchimoto, Daisuke Asakura, Jun Kikkawa, Masanobu Nakayama, Masashi Okubo, Atsuo Yamada^*

^*Corresponding author for this work

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

1 Citation (Scopus)

Abstract

Integrating an anionic-redox (or oxygen-redox) capacity with a conventional cationic-redox capacity is a promising strategy for large-capacity battery cathodes exceeding present technical limits. However, most oxygen-redox cathodes exhibit a large charge/discharge voltage hysteresis (>0.5 V), resulting in poor energy efficiency and impractical implementation. Here, we show that nonpolarizing O⁻ ↔ O²⁻ (4.4 V vs. Li/Li⁺) and polarizing O₂²⁻ → O²⁻ (3.3 V vs. Li/Li⁺) coexist and kinetically compete in O2-type Li_1.12-yNi_0.17Mn_0.71O₂. The oxygen-redox reaction is described as a square scheme, involving bond-forming 2O⁻ → O₂²⁻ and bond-cleaving O₂⁴⁻ → 2O²⁻ processes, where preventing the formation of O₂²⁻ is essential to realize non-polarizing and energy-efficient oxygen-redox reactions.

Original language	English
Pages (from-to)	2591-2600
Number of pages	10
Journal	Energy and Environmental Science
Volume	15
Issue number	6
DOIs	https://doi.org/10.1039/d1ee03503g
Publication status	Published - 2022 May 18
Externally published	Yes

ASJC Scopus subject areas

Environmental Chemistry
Renewable Energy, Sustainability and the Environment
Nuclear Energy and Engineering
Pollution

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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@article{2d58cabe3ab44d8c8c28ec7ecd3daa54,

title = "Kinetic square scheme in oxygen-redox battery electrodes",

abstract = "Integrating an anionic-redox (or oxygen-redox) capacity with a conventional cationic-redox capacity is a promising strategy for large-capacity battery cathodes exceeding present technical limits. However, most oxygen-redox cathodes exhibit a large charge/discharge voltage hysteresis (>0.5 V), resulting in poor energy efficiency and impractical implementation. Here, we show that nonpolarizing O− ↔ O2− (4.4 V vs. Li/Li+) and polarizing O22− → O2− (3.3 V vs. Li/Li+) coexist and kinetically compete in O2-type Li1.12-yNi0.17Mn0.71O2. The oxygen-redox reaction is described as a square scheme, involving bond-forming 2O− → O22− and bond-cleaving O24− → 2O2− processes, where preventing the formation of O22− is essential to realize non-polarizing and energy-efficient oxygen-redox reactions.",

author = "Kosuke Kawai and Shi, {Xiang Mei} and Norio Takenaka and Jeonguk Jang and {de Boisse}, {Benoit Mortemard} and Akihisa Tsuchimoto and Daisuke Asakura and Jun Kikkawa and Masanobu Nakayama and Masashi Okubo and Atsuo Yamada",

note = "Funding Information: This work was financially supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan; Grant-in-Aid for Specially Promoted Research No. 15H05701 and Grant-in-Aid for Scientific Research (S) No. 20H05673. This work was also supported by “Elements Strategy Initiative for Catalysts and Batteries (ESICB)”. M. O. was financially supported by JPSP KAKENHI (Grant Number: 19H05816, 18K19124, and 18H03924), and the Asahi Glass Foundation. M. N. was financially supported by Grant-in-Aid for Scientific Research on Innovative Areas “Interface Ionics” (Grant Number: 19H05815). K. K. was financially supported by JPSP KAKENHI (Grant Number: 20J14291). Soft X-ray absorption/emission spectroscopy at BL07LSU of SPring-8 was performed by joint research in SRRO and ISSP, the University of Tokyo (Proposal No. 2020A7474, 2019B7456, 2019A7452, 2018B7590, 2018A7560, 2018B1514, 2017B1328, and 2016B1503). Soft X-ray absorption/emission spectroscopy at BL27SU of SPring-8 was performed under the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2018A1359). XAFS was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2018G082). Magnetic measurements were performed using facilities of the Cryogenic Research Center, the University of Tokyo. The computations partly conducted in this study have been partly pursued by using the facilities of the Supercomputer Center at the Institute for Solid State Physics at the University of Tokyo. The authors are grateful to J. Miyawaki and Y. Harada at the University of Tokyo and K. Tsuruta and Y. Tamenori at JASRI for their support on the X-ray absorption/emission experiments. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

month = may,

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doi = "10.1039/d1ee03503g",

language = "English",

volume = "15",

pages = "2591--2600",

journal = "Energy and Environmental Science",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Kinetic square scheme in oxygen-redox battery electrodes

AU - Kawai, Kosuke

AU - Shi, Xiang Mei

AU - Takenaka, Norio

AU - Jang, Jeonguk

AU - de Boisse, Benoit Mortemard

AU - Tsuchimoto, Akihisa

AU - Asakura, Daisuke

AU - Kikkawa, Jun

AU - Nakayama, Masanobu

AU - Okubo, Masashi

AU - Yamada, Atsuo

N1 - Funding Information: This work was financially supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan; Grant-in-Aid for Specially Promoted Research No. 15H05701 and Grant-in-Aid for Scientific Research (S) No. 20H05673. This work was also supported by “Elements Strategy Initiative for Catalysts and Batteries (ESICB)”. M. O. was financially supported by JPSP KAKENHI (Grant Number: 19H05816, 18K19124, and 18H03924), and the Asahi Glass Foundation. M. N. was financially supported by Grant-in-Aid for Scientific Research on Innovative Areas “Interface Ionics” (Grant Number: 19H05815). K. K. was financially supported by JPSP KAKENHI (Grant Number: 20J14291). Soft X-ray absorption/emission spectroscopy at BL07LSU of SPring-8 was performed by joint research in SRRO and ISSP, the University of Tokyo (Proposal No. 2020A7474, 2019B7456, 2019A7452, 2018B7590, 2018A7560, 2018B1514, 2017B1328, and 2016B1503). Soft X-ray absorption/emission spectroscopy at BL27SU of SPring-8 was performed under the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2018A1359). XAFS was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2018G082). Magnetic measurements were performed using facilities of the Cryogenic Research Center, the University of Tokyo. The computations partly conducted in this study have been partly pursued by using the facilities of the Supercomputer Center at the Institute for Solid State Physics at the University of Tokyo. The authors are grateful to J. Miyawaki and Y. Harada at the University of Tokyo and K. Tsuruta and Y. Tamenori at JASRI for their support on the X-ray absorption/emission experiments. Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/5/18

Y1 - 2022/5/18

N2 - Integrating an anionic-redox (or oxygen-redox) capacity with a conventional cationic-redox capacity is a promising strategy for large-capacity battery cathodes exceeding present technical limits. However, most oxygen-redox cathodes exhibit a large charge/discharge voltage hysteresis (>0.5 V), resulting in poor energy efficiency and impractical implementation. Here, we show that nonpolarizing O− ↔ O2− (4.4 V vs. Li/Li+) and polarizing O22− → O2− (3.3 V vs. Li/Li+) coexist and kinetically compete in O2-type Li1.12-yNi0.17Mn0.71O2. The oxygen-redox reaction is described as a square scheme, involving bond-forming 2O− → O22− and bond-cleaving O24− → 2O2− processes, where preventing the formation of O22− is essential to realize non-polarizing and energy-efficient oxygen-redox reactions.

AB - Integrating an anionic-redox (or oxygen-redox) capacity with a conventional cationic-redox capacity is a promising strategy for large-capacity battery cathodes exceeding present technical limits. However, most oxygen-redox cathodes exhibit a large charge/discharge voltage hysteresis (>0.5 V), resulting in poor energy efficiency and impractical implementation. Here, we show that nonpolarizing O− ↔ O2− (4.4 V vs. Li/Li+) and polarizing O22− → O2− (3.3 V vs. Li/Li+) coexist and kinetically compete in O2-type Li1.12-yNi0.17Mn0.71O2. The oxygen-redox reaction is described as a square scheme, involving bond-forming 2O− → O22− and bond-cleaving O24− → 2O2− processes, where preventing the formation of O22− is essential to realize non-polarizing and energy-efficient oxygen-redox reactions.

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U2 - 10.1039/d1ee03503g

DO - 10.1039/d1ee03503g

M3 - Article

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SP - 2591

EP - 2600

JO - Energy and Environmental Science

JF - Energy and Environmental Science

SN - 1754-5692

IS - 6

ER -

Kinetic square scheme in oxygen-redox battery electrodes

Abstract

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