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Negative thermal expansion and oxygen-redox electrochemistry

Nature volume 640, pages 941–946 (2025)Cite this article

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Abstract

Structural disorder within materials gives rise to fascinating phenomena, attributed to the intricate interplay of their thermodynamic and electrochemical properties1,2. Oxygen-redox (OR) electrochemistry offers a breakthrough in capacity limits, while inducing structural disorder with reduced electrochemical reversibility3,4,5. The conventional explanation for the thermal expansion of solids relies on the Grüneisen relationship, linking the expansion coefficient to the anharmonicity of the crystal lattice6. However, this paradigm may not be applicable to OR materials due to the unexplored dynamic disorder–order transition in such systems7,8. Here we reveal the presence of negative thermal expansion with a large coefficient value of −14.4(2) × 10−6 °C−1 in OR active materials, attributing this to thermally driven disorder–order transitions. The modulation of OR behaviour not only enables precise control over the thermal expansion coefficient of materials, but also establishes a pragmatic framework for the design of functional materials with zero thermal expansion. Furthermore, we demonstrate that the reinstatement of structural disorder within the material can also be accomplished through the electrochemical driving force. By adjusting the cut-off voltages, evaluation of the discharge voltage change indicates a potential for nearly 100% structure recovery. This finding offers a pathway for restoring OR active materials to their pristine state through operando electrochemical processes, presenting a new mitigation strategy to address the persistent challenge of voltage decay.

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Fig. 1: Probing OR electrochemistry through NTE.
Fig. 2: Controlling OR electrochemistry to tune TEC on different states of delithiation.
Fig. 3: Controlling OR electrochemistry to design ZTE material.
Fig. 4: Electrochemistry-induced disorder–order transition.

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Data availability

The data that supports the findings of this study are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (52272253, 52472266), the External Cooperation Program of the Chinese Academy of Sciences (181GJHZ2024126MI), the ‘Lingyanʼ Research and Development Plan of Zhejiang Province (2022C01071), a Low-Cost Cathode Material (TC220H06P), the R&D Project of Jiangsu Province (BKBG2024021), The “Innovation Yongjiang 2035” Key R&D Program (2025Z063), the Zhongke Hangzhou Bay Institute (Ningbo) New Materials Co. Ltd. (NIMTE-61-2024-2), the Natural Science Foundation of Ningbo (2024QL041) and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2022299). M.Z. and Y.S.M. acknowledge support from the University of Chicago through startup funding. W.W. acknowledges support from the Photon Science Research Center for Carbon Dioxide. We thank beamline BL14B1 of the Shanghai Synchrotron Radiation Facility for providing the beamtime. The authors appreciate the neutron beamtime at the High-resolution Neutron Diffractometer (TREND) (https://cstr.cn/31113.02.CSNS.TREND) and General Purpose Powder Diffractometer (GPPD) (https://csns.cn/31113.02.CSNS.GPPD) at the China Spallation Neutron Source (CSNS) (https://cstr.cn/31113.02.CSNS), and thank W. Ji, S. Deng, F. Shen, Z. Tan, W. Xie, Q. Ma and D. Zhang for their technical assistance during the neutron scattering experiments.

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Author notes

  1. These authors contributed equally: Bao Qiu, Yuhuan Zhou

Authors and Affiliations

  1. Ningbo Institute of Materials Technology and Engineering (NIMTE), Chinese Academy of Sciences (CAS), Ningbo, China

    Bao Qiu, Yuhuan Zhou, Haoyan Liang, Kexin Gu, Zhou Zhou & Zhaoping Liu

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, China

    Bao Qiu, Kexin Gu & Zhaoping Liu

  3. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Minghao Zhang, Sven Burke & Ying Shirley Meng

  4. Shenzhen Graduate School, School of Advanced Materials, Peking University, Shenzhen, China

    Tao Zeng & Yinguo Xiao

  5. Shanghai Synchrotron Radiation Facility, Chinese Academy of Sciences, Shanghai, China

    Wen Wen

  6. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China

    Ping Miao

  7. Spallation Neutron Source Science Center, Dongguan, China

    Ping Miao & Lunhua He

  8. Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Lunhua He

  9. Department of NanoEngineering, University of California San Diego (UCSD), La Jolla, CA, USA

    Ying Shirley Meng

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Contributions

B.Q. conceived the project. B.Q., M.Z., Y.S.M. and Z.L. supervised the project. M.Z. and B.Q. performed the mechanism analysis. Y.Z., K.G., Z.Z. and B.Q. performed the synthesis work. Y.Z. performed the Rietveld refinement for the X-ray and neutron diffraction. Y.Z., K.G. and W.W. performed the X-ray characterization. T.Z., P.M., L.H. and Y.X. performed the neutron characterization. H.L. and B.Q. conducted the voltage recovery. B.Q. and M.Z. prepared the initial draft of the manuscript. S.B. helped revise the manuscript. B.Q., M.Z., Y.S.M. and Z.L. organized the work and helped with the drafting of the manuscript. All the authors discussed the results and approved the final version of the manuscript.

Corresponding authors

Correspondence to Minghao Zhang, Zhaoping Liu or Ying Shirley Meng.

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Qiu, B., Zhou, Y., Liang, H. et al. Negative thermal expansion and oxygen-redox electrochemistry. Nature 640, 941–946 (2025). https://doi.org/10.1038/s41586-025-08765-x

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