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Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries

Nature Sustainability volume 7, pages 348–359 (2024)Cite this article

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Abstract

Sodium-ion batteries are among the most promising alternatives to lithium-based technologies for grid and other energy storage applications due to their cost benefits and sustainable resource supply. For the cathode—the component that largely determines the energy density of a sodium-ion battery cell—one major category of materials is P2-type layered oxides. Unfortunately, at high state-of-charge, such materials tend to undergo a phase transition with a very large volume change and consequent structural degradation during long-term cycling. Here we address this issue by introducing vacancies into the transition metal layer of P2-Na0.7Fe0.1Mn0.75□0.15O2 (‘□’ represents a vacancy). The transition metal vacancy serves to suppress migration of neighbouring Na ions and therefore maintain structural and thermal stability in Na-depleted states. Moreover, the specific Na−O−□ configuration triggers a reversible anionic redox reaction and boosts the energy density. As a result, the cathode design here enables pouch cells with energy densities of 170 Wh kg−1 and 120 Wh kg−1 that can operate for over 600 and 1,000 cycles, respectively. Our work not only suggests a feasible strategy for cathode design but also confirms the possibility of developing a battery chemistry that features a reduced need for critical raw materials.

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Fig. 1: Illustration of the P-to-O phase transition.
Fig. 2: Intrinsic vacancies and the anionic redox reaction in NFMOs.
Fig. 3: Structural evolution during the first charging–discharging process of NFMOs.
Fig. 4: Revealing the mechanisms of intrinsic vacancies via ML-AIMD.
Fig. 5: Comparison of the electrochemical performances of VF-NFMO and VC-NFMO.

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Data availability

The data that support the findings detailed in this study are available in the article and its Supplementary Information or from the corresponding authors on reasonable request. The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC). Source data are provided with this paper.

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Acknowledgements

This work was partially supported by the National Natural Science Foundation of China (grants 22021001, 22179111, 22109186, 22272022, 52122211 and 52072323), the Ministry of Science and Technology of China (grants 2023YFB2406200 and 2021YFA1201900), the Basic Research Program of Tan Kah Kee Innovation Laboratory (grant RD2021070401), the Principal Fund from Xiamen University (grant 20720210015), the Fundamental Research Funds for the Central Universities (grant 20720220010) and the Beijing Natural Science Foundation (grant Z190010). This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. G.-L.X. and K.A. thank the Clean Vehicle Consortium, US–China Clean Energy Research Centre (CERC-CVC2) for support. Part of this work was conducted at the NOMAD beamline at the Spallation Neutron Source, Oak Ridge National Laboratory, which is sponsored by the Scientific User Facilities Division, Office of Basic Sciences, US Department of Energy. This research also employed the resources of the Shanghai Synchrotron Radiation Facility BL02B02, BL11B, BL14B1 and BL14W1 beamline stations (SSRF, under contracts 2021-SSRF-PT-017208, 2022-SSRF-PT-019758, 2022-SSRF-PT-021637 and 2023-SSRF-ZD-503448); beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at Hefei National Synchrotron Radiation Laboratory (NSRL-USTC, under contracts 2021-HLS-PT-004529, 2021-HLS-PT-004156 and 2021-HLS-PT-004241); Beijing Synchrotron Radiation Laboratory 1W1A, 1W1B, 3W1, 4B9A and 4B9B beamline stations (under contracts 2021-BEPC-PT-005771, 2021-BEPC-PT-005765, 2021-BEPC-PT-005760 and 2022-BEPC-PT-006478) and Multi-Physics Instrument at China Spallation Neutron Source (MPI, CSNS, under contracts P1621080200036 and P1621122000008). We appreciate the help from D. Wong, C. Schulz and M. Bartkowiak for the RIXS characterization (proposal-Info: 221-11099-ST) at beamline U41-PEAXIS of Bessy II, Helmholtz-Zentrum Berlin für Materialien und Energie (HZB), Berlin, Germany. We thank W. He (Chimie du Solide-Energie, Collège de France, France), S. Yang (Department of Materials, University of Oxford, U.K.), L. Pan (Hokkaido University, Japan), H. Li (University of Illinois at Chicago, USA) and J. Serrano Sevillano (CIC Energi Gune, Spain) for their help and discussion on in situ XRD, OEMS, Moss, nPDF characterizations and FAULTS programme.

Author information

Author notes

  1. These authors contributed equally: Yonglin Tang, Qinghua Zhang, Wenhua Zuo, Shiyuan Zhou.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, PR China

    Yonglin Tang, Shiyuan Zhou, Guifan Zeng, Baodan Zhang, Haitang Zhang, Qiaobao Zhang, Tiqing Zhao, Hong-Gang Liao, Yu Qiao & Shi-Gang Sun

  2. Institute of Physics, Chinese Academy of Sciences, Beijing, PR China

    Qinghua Zhang

  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Wenhua Zuo, Shiyuan Zhou, Khalil Amine & Gui-Liang Xu

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

    Zhongyuan Huang & Yinguo Xiao

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

    Lirong Zheng, Juping Xu & Wen Yin

  6. Spallation Neutron Source Science Center, Dongguan, China

    Juping Xu & Wen Yin

  7. School of Materials Science and Engineering, Dongguan University of Technology, Guangdong, PR China

    Yongfu Qiu

  8. X-ray Sciences Division, Argonne National Laboratory, Lemont, IL, USA

    Inhui Hwang & Cheng-Jun Sun

  9. Bavarian Center for Battery Technology (BayBatt), Department of Chemistry, University of Bayreuth, Bayreuth, Germany

    Qingsong Wang

  10. School of Materials, Sun Yat-sen University, Shenzhen, China

    Yang Sun

  11. School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Lin Gu

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  1. Yonglin Tang
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Contributions

Y.T. and Y. Qiao contributed to the design of the research and performed the experimental data analysis. Y.T. conducted the materials synthesis, electrochemistry and cell performance. Qinghua Zhang and L.G. conducted the STEM experiments and related data analysis. W.Z. and L.Z. conducted the hard-XAS experiments with the help of I.H. and C.-J.S. Y.T. conducted the analysis of XAS results with the help of L.Z., G.-L.X. and K.A. B.Z. and G.Z. helped to conduct the XRD experiment and FAULTS simulation. Z.H., J.X., Y. Qiu, W.Y. and Y.X. conducted the NPD/nPDF experiments and related data analysis. H.Z. conducted the in situ heated MS experiments. T.Z. and S.Z. conducted the in situ heated TEM experiments and related data analysis with the help of Qiaobao Zhang and H.-G.L. Q.W. conducted the RIXS experiments and related data analysis. Y.S. conducted the theoretical calculation and related data analysis. Y. Qiao conducted the analysis of Fe-MS characterizations. Q.W., Y.S., G.-L.X., L.G., Y. Qiao and S.-G.S. supervised the work. All authors discussed the results, co-wrote and commented on the manuscript.

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Correspondence to Qingsong Wang, Yang Sun, Gui-Liang Xu, Lin Gu or Yu Qiao.

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Extended data

Extended Data Fig. 1 Charge compensation mechanism and TM − O coordination environment analysis of NFMOs.

a, X-ray absorption near edge structure (XANES) of the Fe K-edge (left) and Mn K-edge (right) of VC-NFMO collected at different states of charge/discharge; Fe2+/Fe3+ and Mn2+/Mn3+/Mn4+ standard spectra are shown at the bottom for comparison. b, Fourier transforms (FTs) of the Fe K-edge (left) and Mn K-edge (right) EXAFS spectra of VC-NFMO collected at different states of charge/discharge. The spectra have been offset for clear visibility, and the EXAFS spectra (Fe and Mn) collected in the OCV state have also been offset and overlaid as grey dashed lines for comparison. c, Redox state analysis of VF-NFMO (grey) and VC-NFMO (blue) in various charge/discharge states. The average edge position is fitted by the integral method. The Fe K-edge (top) and Mn K-edge (bottom) edge positions are directly fitted for the corresponding XANES edge regions shown in Supplementary Fig. 18 and (a). d, EXAFS fitting results of VF-NFMO (grey) and VC-NFMO (blue) in various charge/discharge states. The TM − O and TM − TM distances of the Fe K-edge (top) and Mn K-edge (bottom) are fitted for the corresponding FT EXAFS regions shown in Supplementary Fig. 20 and (b). The error bars represent the error range during EXAFS fitting and the precise values are given in Supplementary Tables 12–13. e, Wavelet transform (WT)-EXAFS differential spectra of the Fe-K edge of both VF-NFMO (left) and VC-NFMO (right) between the OCV and 4.5 V. The change from purple to red indicates a greater difference in the Fe K-edge. f, Schematic of the TM − O/TM − TM covalent structural distortion induced by the P-to-O phase transition in VF-NFMO.

Source data

Extended Data Fig. 2 Structural, morphological, and gas evolution of the charged cathodes at high temperatures.

a, Schematic of the charged P2-type cathode characterized by in situ XRD, MS, and TEM under thermal runaway simulation. b,c, Results of in situ XRD and online electrochemical mass spectrometry (OEMS) of the 4.5 V-charged (b) VF-NFMO and (c) VC-NFMO cathode plates upon heating from room temperature to 400 °C at 5 °C min−1. d,e, SAED patterns of the (d) VF-NFMO and (e) VC-NFMO cathode powders scraped from the 4.5 V-charged cathode plates during heating from room temperature to 400 °C at 2 °C s−1. Scale bars, 5 nm−1.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1−28, Tables 1−14 and Notes 1 and 2.

Reporting Summary

Supplementary Video 1

In situ selected area electron diffraction (SAED) of the 4.5 V charged VF-NFMO during heating from room temperature to 400 °C at 2 °C s–1 (displayed with a speed ×10 of a real-time process).

Supplementary Video 2

In situ SAED of the 4.5 V charged VC-NFMO during heating from room temperature to 400 °C at 2 °C s–1 (displayed with a speed ×30 of a real-time process).

Supplementary Video 3

In situ transmission electron microscope (TEM) of the 4.5 V charged VC-NFMO upon heating from room temperature to 700 °C at 2 °C s–1 (displayed with a speed ×30 of a real-time process).

Supplementary Video 4

In situ TEM of the 4.5 V charged VF-NFMO upon heating from room temperature to 700 °C at 2 °C s–1 (displayed with a speed ×10 of a real-time process).

Source data

Source Data Fig. 1

FAULTS simulations results.

Source Data Fig. 2

Structure characterization results.

Source Data Fig. 3

Structural evolution characterization results.

Source Data Fig. 4

Machine learning-aided ab initio molecular dynamics simulations.

Source Data Fig. 5

Electrochemical results.

Source Data Extended Data Fig. 1

X-ray absorption spectrum results.

Source Data Extended Data Fig. 2

Structural evolution under thermal runaway.

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Tang, Y., Zhang, Q., Zuo, W. et al. Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries. Nat Sustain 7, 348–359 (2024). https://doi.org/10.1038/s41893-024-01288-9

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