Temperature-Dependent Dynamic Disproportionation in LiNiO2

Andrey D. Poletayev; Robert J. Green; Jack E. N. Swallow; Lijin An; Leanne Jones; Grant Harris; Peter Bencok; Ronny Sutarto; Jonathon P. Cottom; Benjamin J. Morgan; Robert A. House; Robert S. Weatherup; M. Saiful Islam

doi:10.1038/s41467-025-64429-4

Temperature-Dependent Dynamic Disproportionation in LiNiO₂

Andrey D. Poletayev, Robert J. Green, Jack E. N. Swallow, Lijin An, Leanne Jones, Grant Harris, Peter Bencok, Ronny Sutarto, Jonathon P. Cottom, Benjamin J. Morgan, Robert A. House, Robert S. Weatherup, M. Saiful Islam

Department of Chemistry

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Abstract

Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO₂) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here, we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO₂. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L3,2-edge. Charge transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO₂, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO₂ is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.

Original language	English
Article number	9379
Journal	Nature Communications
Volume	16
DOIs	https://doi.org/10.1038/s41467-025-64429-4
Publication status	Published - 23 Oct 2025

Data Availability Statement

Computed Ni L3,2-edge spectral shapes, computed Ni L3,2-edge RIXS spectra, experimental IPFY and RIXS spectra, and exemplar ab initio molecular dynamics trajectories with setup files are available at reference68.

Acknowledgements

Part of the research described in this paper was performed at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. A.D.P. is grateful to Dr. Pezhman Zarabadi-Poor and Dr. Gregory Rees for insightful discussions.

Funding

The authors acknowledge funding from the UK Faraday Institution (faraday.ac.uk; EP/S003053/1, FIRG016, FIRG024, FIRG030) and the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (EXISTAR, grant agreement No. 950598). B.J.M. acknowledges support from the Royal Society (URF/R/191006). R.S.W. acknowledges a CAMS-UK Fellowship through the Analytical Chemistry Trust Fund and a UKRI Future Leaders Fellowship (MR/V024558/1). R.J.G. and G.H. acknowledge funding from the Natural Sciences and Engineering Research Council of Canada (NSERC). The authors acknowledge the HEC Materials Chemistry Consortium (EP/R029431) for the use of Archer2 high-performance computing (HPC) facilities. The authors also acknowledge the Faraday Institution’s Michael HPC resource. We acknowledge Diamond Light Source for time on beamlines I10 and I21 under proposals MM33062 and MM30644-1, and Dr. Stefano Agrestini, Dr. Mirian Garcia-Fernandez, and Dr. Ke-Jin Zhou for assistance with the RIXS measurements.

UN SDGs

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

SDG 7 Affordable and Clean Energy

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10.1038/s41467-025-64429-4Licence: CC BY

240624 LiNiO2 arXivSubmitted manuscript, 3.65 MBLicence: CC BY

https://arxiv.org/abs/2211.09047Licence: CC BY-NC-ND

Cite this

@article{4db22663bfdd47649bc22e697850c8fa,

title = "Temperature-Dependent Dynamic Disproportionation in LiNiO2",

abstract = "Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO2) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here, we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO2. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L3,2-edge. Charge transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO2, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO2 is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors. ",

author = "Poletayev, \{Andrey D.\} and Green, \{Robert J.\} and Swallow, \{Jack E. N.\} and Lijin An and Leanne Jones and Grant Harris and Peter Bencok and Ronny Sutarto and Cottom, \{Jonathon P.\} and Morgan, \{Benjamin J.\} and House, \{Robert A.\} and Weatherup, \{Robert S.\} and Islam, \{M. Saiful\}",

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doi = "10.1038/s41467-025-64429-4",

language = "English",

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AU - Swallow, Jack E. N.

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AU - Jones, Leanne

AU - Harris, Grant

AU - Bencok, Peter

AU - Sutarto, Ronny

AU - Cottom, Jonathon P.

AU - Morgan, Benjamin J.

AU - House, Robert A.

AU - Weatherup, Robert S.

AU - Islam, M. Saiful

PY - 2025/10/23

Y1 - 2025/10/23

N2 - Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO2) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here, we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO2. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L3,2-edge. Charge transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO2, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO2 is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.

AB - Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO2) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here, we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO2. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L3,2-edge. Charge transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO2, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO2 is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.

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JO - Nature Communications

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Temperature-Dependent Dynamic Disproportionation in LiNiO₂

Abstract

Data Availability Statement

Acknowledgements

Funding

UN SDGs

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CATMAT phase 2

Next Generation Li-ion Cathode Materials (CAT-MAT)

Cite this

Temperature-Dependent Dynamic Disproportionation in LiNiO2

Abstract

Data Availability Statement

Acknowledgements

Funding

UN SDGs

Access to Document

Other files and links

Fingerprint

Projects

CATMAT phase 2

Next Generation Li-ion Cathode Materials (CAT-MAT)

Cite this

Temperature-Dependent Dynamic Disproportionation in LiNiO₂