Unveiling the Origin of Oxygen Framework Stability in Ultra-High Nickel Layered Oxide Cathodes

Fangyan Liu; Shihao Li; Chihon Leung; Xiaozhi Jiang; Han Liu; Tianyi Li; Qi Liu; Gang Sun; Zhenbo Wang; Zhian Zhang; Yanqing Lai; Yang Ren; Jiayi Yang

doi:10.1002/adma.202419856

Unveiling the Origin of Oxygen Framework Stability in Ultra-High Nickel Layered Oxide Cathodes

Fangyan Liu, Shihao Li, Chihon Leung, Xiaozhi Jiang, Han Liu, Tianyi Li, Qi Liu, Gang Sun, Zhenbo Wang, Zhian Zhang^*, Yanqing Lai^*, Yang Ren^*, Jiayi Yang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

2 Citations (Scopus)

Abstract

Ultra-high nickel layered oxides are recognized as promising cathode candidates for high-energy-density lithium-ion batteries due to their enhanced overall capacity and elevated operating voltage. However, the interlayer sliding of transition metal-oxygen octahedra (TMO6) and the instability of lattice oxygen at high voltages for ultra-high nickel oxide cathodes pose significant challenges to their development. Herein, the origin of oxygen framework stability is investigated by incorporating high-covalent element Mo in both bulk and surface using a one-step integrated method for ultra-high nickel cathode material LiNi_0.92Co_0.08O₂. It is revealed that apart from the isolation and protection effect of the Mo-enriched surface layer, the suppression of Li/Ni antisite defects by Mo⁶⁺ with strong covalency in the bulk plays a critical role in reducing the configurations of the activated anionic redox reaction and stabilizing the lattice oxygen and oxygen framework structure. Benefiting from this, the reversibility of anionic redox reaction and the stability of oxygen framework is significantly enhanced, enabling more oxidized oxygen to exist in the form of oxygen dimer ions (Formula presented.) rather than being lost as gaseous O₂. Consequently, the modified ultra-high nickel material demonstrates improved diffusion kinetics and optimized electrochemical performance at high voltage. © 2025 Wiley-VCH GmbH.

Original language	English
Article number	2419856
Journal	Advanced Materials
Volume	37
Issue number	15
Online published	6 Mar 2025
DOIs	https://doi.org/10.1002/adma.202419856
Publication status	Published - 16 Apr 2025

Funding

F.L. and S.L. contributed equally to this work. The authors acknowledge the Shenzhen Science and Technology Innovation Commission (JCYJ20220818101016034), City University of Hong Kong (CityU 9610533), and the Shenzhen Research Institute, City University of Hong Kong. One of the authors (YR) would like to express his sincere appreciation to the Hong Kong SAR for supporting the research under the Global STEM Professorship. The research work described in this paper was conducted in the JC STEM Lab of Energy and Materials Physics funded by The Hong Kong Jockey Club Charities Trust.

Research Keywords

anionic redox reaction
high voltage
lattice oxygen framework
structural stability
ultra-high nickel cathode

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abstract = "Ultra-high nickel layered oxides are recognized as promising cathode candidates for high-energy-density lithium-ion batteries due to their enhanced overall capacity and elevated operating voltage. However, the interlayer sliding of transition metal-oxygen octahedra (TMO6) and the instability of lattice oxygen at high voltages for ultra-high nickel oxide cathodes pose significant challenges to their development. Herein, the origin of oxygen framework stability is investigated by incorporating high-covalent element Mo in both bulk and surface using a one-step integrated method for ultra-high nickel cathode material LiNi0.92Co0.08O2. It is revealed that apart from the isolation and protection effect of the Mo-enriched surface layer, the suppression of Li/Ni antisite defects by Mo6+ with strong covalency in the bulk plays a critical role in reducing the configurations of the activated anionic redox reaction and stabilizing the lattice oxygen and oxygen framework structure. Benefiting from this, the reversibility of anionic redox reaction and the stability of oxygen framework is significantly enhanced, enabling more oxidized oxygen to exist in the form of oxygen dimer ions (Formula presented.) rather than being lost as gaseous O2. Consequently, the modified ultra-high nickel material demonstrates improved diffusion kinetics and optimized electrochemical performance at high voltage. {\textcopyright} 2025 Wiley-VCH GmbH.",

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author = "Fangyan Liu and Shihao Li and Chihon Leung and Xiaozhi Jiang and Han Liu and Tianyi Li and Qi Liu and Gang Sun and Zhenbo Wang and Zhian Zhang and Yanqing Lai and Yang Ren and Jiayi Yang",

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AU - Liu, Fangyan

AU - Li, Shihao

AU - Leung, Chihon

AU - Jiang, Xiaozhi

AU - Liu, Han

AU - Li, Tianyi

AU - Liu, Qi

AU - Sun, Gang

AU - Wang, Zhenbo

AU - Zhang, Zhian

AU - Lai, Yanqing

AU - Ren, Yang

AU - Yang, Jiayi

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N2 - Ultra-high nickel layered oxides are recognized as promising cathode candidates for high-energy-density lithium-ion batteries due to their enhanced overall capacity and elevated operating voltage. However, the interlayer sliding of transition metal-oxygen octahedra (TMO6) and the instability of lattice oxygen at high voltages for ultra-high nickel oxide cathodes pose significant challenges to their development. Herein, the origin of oxygen framework stability is investigated by incorporating high-covalent element Mo in both bulk and surface using a one-step integrated method for ultra-high nickel cathode material LiNi0.92Co0.08O2. It is revealed that apart from the isolation and protection effect of the Mo-enriched surface layer, the suppression of Li/Ni antisite defects by Mo6+ with strong covalency in the bulk plays a critical role in reducing the configurations of the activated anionic redox reaction and stabilizing the lattice oxygen and oxygen framework structure. Benefiting from this, the reversibility of anionic redox reaction and the stability of oxygen framework is significantly enhanced, enabling more oxidized oxygen to exist in the form of oxygen dimer ions (Formula presented.) rather than being lost as gaseous O2. Consequently, the modified ultra-high nickel material demonstrates improved diffusion kinetics and optimized electrochemical performance at high voltage. © 2025 Wiley-VCH GmbH.

AB - Ultra-high nickel layered oxides are recognized as promising cathode candidates for high-energy-density lithium-ion batteries due to their enhanced overall capacity and elevated operating voltage. However, the interlayer sliding of transition metal-oxygen octahedra (TMO6) and the instability of lattice oxygen at high voltages for ultra-high nickel oxide cathodes pose significant challenges to their development. Herein, the origin of oxygen framework stability is investigated by incorporating high-covalent element Mo in both bulk and surface using a one-step integrated method for ultra-high nickel cathode material LiNi0.92Co0.08O2. It is revealed that apart from the isolation and protection effect of the Mo-enriched surface layer, the suppression of Li/Ni antisite defects by Mo6+ with strong covalency in the bulk plays a critical role in reducing the configurations of the activated anionic redox reaction and stabilizing the lattice oxygen and oxygen framework structure. Benefiting from this, the reversibility of anionic redox reaction and the stability of oxygen framework is significantly enhanced, enabling more oxidized oxygen to exist in the form of oxygen dimer ions (Formula presented.) rather than being lost as gaseous O2. Consequently, the modified ultra-high nickel material demonstrates improved diffusion kinetics and optimized electrochemical performance at high voltage. © 2025 Wiley-VCH GmbH.

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KW - high voltage

KW - lattice oxygen framework

KW - structural stability

KW - ultra-high nickel cathode

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Unveiling the Origin of Oxygen Framework Stability in Ultra-High Nickel Layered Oxide Cathodes

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