Transition metal vacancy and position engineering enables reversible anionic redox reaction for sodium storage

Congcong Cai; Xinyuan Li; Jiantao Li; Ruohan Yu; Ping Hu; Ting Zhu; Tianyi Li; Sungsik Lee; Nuo Xu; Hao Fan; Jinsong Wu; Liang Zhou; Liqiang Mai; Khalil Amine

doi:10.1038/s41467-024-54998-1

Transition metal vacancy and position engineering enables reversible anionic redox reaction for sodium storage

Congcong Cai, Xinyuan Li, Jiantao Li^*, Ruohan Yu, Ping Hu, Ting Zhu, Tianyi Li, Sungsik Lee, Nuo Xu, Hao Fan, Jinsong Wu, Liang Zhou^*, Liqiang Mai^*, Khalil Amine^*

^*Corresponding author for this work

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

Abstract

Triggering the anionic redox reaction is an effective approach to boost the capacity of layered transition metal (TM) oxides. However, the irreversible oxygen release and structural deterioration at high voltage remain conundrums. Herein, a strategy for Mg ion and vacancy dual doping with partial TM ions pinned in the Na layers is developed to improve both the reversibility of anionic redox reaction and structural stability of layered oxides. Both the Mg ions and vacancies (□) are contained in the TM layers, while partial Mn ions (~1.1%) occupy the Na-sites. The introduced Mg ions combined with vacancies not only create abundant nonbonding O 2p orbitals in favor of high oxygen redox capacity, but also suppress the voltage decay originated from Na–O–□ configuration. The Mn ions pinned in the Na layers act as “rivets” to restrain the slab gliding at extreme de-sodiated state and thereby inhibit the generation of cracks. The positive electrode, Na_0.67Mn_0.011[Mg_0.1□_0.07Mn_0.83]O₂, delivers an enhanced discharge capacity and decent cyclability. This study provides insights into the construction of stable layered oxide positive electrode with highly reversible anionic redox reaction for sodium storage.

Original language	English (US)
Article number	100
Journal	Nature communications
Volume	16
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-54998-1
State	Published - Dec 2025

Funding

This work was supported by the National Key Research and Development Program of China (2020YFA0715000, L.M.) and the National Natural Science Foundation of China (U23A20684, L.Z.). This work gratefully acknowledges support from the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. This research used resources of the Advanced Photon Source (beamline 12-BM-B), a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02- 06CH11357. The STEM was performed at the Nanostructure Research Center (NRC).

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

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10.1038/s41467-024-54998-1

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title = "Transition metal vacancy and position engineering enables reversible anionic redox reaction for sodium storage",

abstract = "Triggering the anionic redox reaction is an effective approach to boost the capacity of layered transition metal (TM) oxides. However, the irreversible oxygen release and structural deterioration at high voltage remain conundrums. Herein, a strategy for Mg ion and vacancy dual doping with partial TM ions pinned in the Na layers is developed to improve both the reversibility of anionic redox reaction and structural stability of layered oxides. Both the Mg ions and vacancies (□) are contained in the TM layers, while partial Mn ions (~1.1%) occupy the Na-sites. The introduced Mg ions combined with vacancies not only create abundant nonbonding O 2p orbitals in favor of high oxygen redox capacity, but also suppress the voltage decay originated from Na–O–□ configuration. The Mn ions pinned in the Na layers act as “rivets” to restrain the slab gliding at extreme de-sodiated state and thereby inhibit the generation of cracks. The positive electrode, Na0.67Mn0.011[Mg0.1□0.07Mn0.83]O2, delivers an enhanced discharge capacity and decent cyclability. This study provides insights into the construction of stable layered oxide positive electrode with highly reversible anionic redox reaction for sodium storage.",

author = "Congcong Cai and Xinyuan Li and Jiantao Li and Ruohan Yu and Ping Hu and Ting Zhu and Tianyi Li and Sungsik Lee and Nuo Xu and Hao Fan and Jinsong Wu and Liang Zhou and Liqiang Mai and Khalil Amine",

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doi = "10.1038/s41467-024-54998-1",

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T1 - Transition metal vacancy and position engineering enables reversible anionic redox reaction for sodium storage

AU - Cai, Congcong

AU - Li, Xinyuan

AU - Li, Jiantao

AU - Yu, Ruohan

AU - Hu, Ping

AU - Zhu, Ting

AU - Li, Tianyi

AU - Lee, Sungsik

AU - Xu, Nuo

AU - Fan, Hao

AU - Wu, Jinsong

AU - Zhou, Liang

AU - Mai, Liqiang

AU - Amine, Khalil

PY - 2025/12

Y1 - 2025/12

N2 - Triggering the anionic redox reaction is an effective approach to boost the capacity of layered transition metal (TM) oxides. However, the irreversible oxygen release and structural deterioration at high voltage remain conundrums. Herein, a strategy for Mg ion and vacancy dual doping with partial TM ions pinned in the Na layers is developed to improve both the reversibility of anionic redox reaction and structural stability of layered oxides. Both the Mg ions and vacancies (□) are contained in the TM layers, while partial Mn ions (~1.1%) occupy the Na-sites. The introduced Mg ions combined with vacancies not only create abundant nonbonding O 2p orbitals in favor of high oxygen redox capacity, but also suppress the voltage decay originated from Na–O–□ configuration. The Mn ions pinned in the Na layers act as “rivets” to restrain the slab gliding at extreme de-sodiated state and thereby inhibit the generation of cracks. The positive electrode, Na0.67Mn0.011[Mg0.1□0.07Mn0.83]O2, delivers an enhanced discharge capacity and decent cyclability. This study provides insights into the construction of stable layered oxide positive electrode with highly reversible anionic redox reaction for sodium storage.

AB - Triggering the anionic redox reaction is an effective approach to boost the capacity of layered transition metal (TM) oxides. However, the irreversible oxygen release and structural deterioration at high voltage remain conundrums. Herein, a strategy for Mg ion and vacancy dual doping with partial TM ions pinned in the Na layers is developed to improve both the reversibility of anionic redox reaction and structural stability of layered oxides. Both the Mg ions and vacancies (□) are contained in the TM layers, while partial Mn ions (~1.1%) occupy the Na-sites. The introduced Mg ions combined with vacancies not only create abundant nonbonding O 2p orbitals in favor of high oxygen redox capacity, but also suppress the voltage decay originated from Na–O–□ configuration. The Mn ions pinned in the Na layers act as “rivets” to restrain the slab gliding at extreme de-sodiated state and thereby inhibit the generation of cracks. The positive electrode, Na0.67Mn0.011[Mg0.1□0.07Mn0.83]O2, delivers an enhanced discharge capacity and decent cyclability. This study provides insights into the construction of stable layered oxide positive electrode with highly reversible anionic redox reaction for sodium storage.

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Transition metal vacancy and position engineering enables reversible anionic redox reaction for sodium storage

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