Recovery of High-Voltage Oxygen Redox Activity by Eliminating Residual Oxygen Dimers

Oxygen-redox layered oxides are promising electrode materials with the potential for superior energy density; however, their real-world employment is hindered by severe electrochemical irreversibility. The fundamental origin of this irreversibility has been difficult to pinpoint due to the complex evolution of both the structure and redox centers during cycling. Herein, we reveal that oxygen redox irreversibility is governed by the formation and persistence of oxygen dimer states and, for the first time, demonstrate the reversible recovery of the intrinsic high-voltage oxygen redox plateau (∼4.5 V vs Li/Li<sup>+</sup>), which is typically lost after initial charge. Our in-depth tracking of oxygen dimer behavior establishes a direct correlation between the recoverability of the high-voltage plateau and the residual concentration of oxygen dimers in the electrode material. Furthermore, we identify sluggish dimer dissociation kinetics as the root cause of the irreversible loss of high-voltage oxygen redox activity. More importantly, we demonstrate that these kinetically trapped oxygen dimers can be eliminated by facilitating electron transfer from transition metal to oxygen dimers via redox reshuffling at a moderately elevated temperature, thereby fully restoring the high-voltage oxygen redox activity. These findings clarify the role of oxygen dimer kinetics in redox irreversibility and provide valuable insights toward achieving voltage-hysteresis-free anionic redox in oxygen redox electrodes.

Authors

Institutions

Publication Details

Journal
Journal of the American Chemical Society
Published
2025-10-15
DOI
https://doi.org/10.1021/jacs.5c11310
Citations
1
Primary Topic
Fuel Cells and Related Materials
Type
article
Field-Weighted Citation Impact
0.73
Controls
|||
ALL TIME
JAN
FEB
MAR
APR
MAY
JUN
JUL
AUG
SEP
OCT
article

Recovery of High-Voltage Oxygen Redox Activity by Eliminating Residual Oxygen Dimers

Kyoungoh Kim, Hojoon Lim, Jonghun Park, Ho‐Young Jang et al.
1 citations
Journal of the American Chemical Society
Fuel Cells and Related Materials
0.73
article

Recovery of High-Voltage Oxygen Redox Activity by Eliminating Residual Oxygen Dimers

Kyoungoh Kim, Hojoon Lim, Jonghun Park, Ho‐Young Jang, Akhil Tayal, Jihyeon Kim, He Jin, Youngsin Kim, Donggun Eum, Chaelin Lee, Byung-Wook Kang, Kun‐Hee Ko, Okkyun Seo, Joohyeon Noh, Kisuk Kang, Dae Soo Jung, Saki Imada, Juhan Lee, Jooha Park, Sung O Park, Seongmin Kang, H. S. Ahn, Young-Jun Jeon, H.M. Kim, Sung-Pyo Cho
article en
1 citations

Abstract

Oxygen-redox layered oxides are promising electrode materials with the potential for superior energy density; however, their real-world employment is hindered by severe electrochemical irreversibility. The fundamental origin of this irreversibility has been difficult to pinpoint due to the complex evolution of both the structure and redox centers during cycling. Herein, we reveal that oxygen redox irreversibility is governed by the formation and persistence of oxygen dimer states and, for the first time, demonstrate the reversible recovery of the intrinsic high-voltage oxygen redox plateau (∼4.5 V vs Li/Li<sup>+</sup>), which is typically lost after initial charge. Our in-depth tracking of oxygen dimer behavior establishes a direct correlation between the recoverability of the high-voltage plateau and the residual concentration of oxygen dimers in the electrode material. Furthermore, we identify sluggish dimer dissociation kinetics as the root cause of the irreversible loss of high-voltage oxygen redox activity. More importantly, we demonstrate that these kinetically trapped oxygen dimers can be eliminated by facilitating electron transfer from transition metal to oxygen dimers via redox reshuffling at a moderately elevated temperature, thereby fully restoring the high-voltage oxygen redox activity. These findings clarify the role of oxygen dimer kinetics in redox irreversibility and provide valuable insights toward achieving voltage-hysteresis-free anionic redox in oxygen redox electrodes.

Journal of the American Chemical SocietyVol. 147(43)
Seoul National University (KR), Brookhaven National Laboratory (US), Kyoto Institute of Technology (JP), Institute for Basic Science (KR), Korea Institute of Ceramic Engineering and Technology (KR), Japan Synchrotron Radiation Research Institute (JP), Integrative Medicine Institute (US), Myongji University (KR), Stanford University (US)
Openalex Percentile: Top 22%
Fuel Cells and Related Materials
0.73
DOIOpen Access PDFOpenAlex
AI Navigator

Ask Laika to Summarize, Analyze, and Connect papers live on the map.

Summarize Papers & Methodologies

Extract key findings, datasets, and comparative methods across publications.

Benchmark Rankings & Visual Analytics

Rank top research institutions, authors, funders, topics, and journals by Field-Weighted Citation Impact (FWCI) and paper volume with instant charts.

Connect Distant Disciplines

Bridge topological clusters on the map to find hidden collaborative intersections.