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A cathode homogenization strategy for enabling long-cycle-life all-solid-state lithium batteries

Nature Energy volume 9, pages 1084–1094 (2024) Cite this article

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Abstract

All-solid-state lithium batteries typically employ heterogeneous composite cathodes where conductive additives are introduced to improve mixed conduction. These electrochemically inactive additives are not fully compatible with layered oxide cathodes that undergo large volume change, significantly reducing battery energy density and cycle life. Here we propose a cathode homogenization strategy by cold pressing a zero-strain cathode material with efficient mixed conduction throughout the (dis)charge process. Li1.75Ti2(Ge0.25P0.75S3.8Se0.2)3 possesses considerable Li+/electronic conductivity of 0.22/242 mS cm−1 when fully charged, increasing monotonically to 0.66/412 mS cm−1 when fully discharged. It delivers a specific capacity of 250 mAh g−1 and undergoes a 1.2% volume change. Homogeneous cathodes composed of 100% Li1.75Ti2(Ge0.25P0.75S3.8Se0.2)3 enable room-temperature all-solid-state lithium batteries to achieve a cycle life of over 20,000 cycles at 2.5 C with a specific capacity retention of 70% and a high energy density of 390 Wh kg−1 at the cell level at 0.1 C. This cathode homogenization strategy contrasts to the conventional cathode heterogeneous design, potentially improving the viability of all-solid-state lithium batteries for commercial applications.

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Fig. 1: Schematic illustration of cathode microstructure evolution during charging.
The alternative text for this image may have been generated using AI.
Fig. 2: Structure, morphology and conductivity of Se-tuned LTG0.25PS.
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Fig. 3: Structure and conductivity evolution of LTG0.25PSSe0.2 with Li+ extraction/insertion.
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Fig. 4: Demonstration of LTG0.25PSSe0.2 as a homogeneous cathode in ASLBs.
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Fig. 5: Long cycling stability and lithiation dynamics of LTG0.25PSSe0.2.
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Data availability

The data supporting the findings of this study are available within the paper, Supplementary Information and source data. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2023YFC2812700, G.C.), the National Natural Science Foundation of China (52372245, J.J.; 22139001, G.C.; 52037006, G.C.), the Natural Science Foundation of Shandong Province (ZR2023ME027, J.J.; ZR2022QB160, S.Z.; ZR2022QB172, T.L.), Key Scientific and Technological Innovation Project of Shandong (2022CXGC020301, G.C.; 2023CXGC010302, G.C.), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA22010604, G.C.), the Taishan Scholars of Shandong Province (number ts201511063, G.C.; number tsqn202306308, J.M.) and Qingdao New Energy Shandong Laboratory (QIBEBT/SEI/QNESLS202304, G.C.) and the Emerging Industry Cultivation Plan of Qingdao Future Industry Cultivation Project (number 24-1-4-xxgg-7-gx, G.C.). We acknowledge support from the Max Planck-POSTECH-Hsinchu Center for Complex Materials.

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  1. These authors contributed equally: Longfei Cui, Shu Zhang.

Authors and Affiliations

  1. Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, China

    Longfei Cui, Shu Zhang, Jiangwei Ju, Tao Liu, Yue Zheng, Jiahao Xu, Yantao Wang, Jiedong Li, Jingwen Zhao, Jun Ma, Jinzhi Wang, Gaojie Xu & Guanglei Cui

  2. Shandong Energy Institute, Qingdao, China

    Longfei Cui, Shu Zhang, Jiangwei Ju, Jingwen Zhao, Jun Ma & Guanglei Cui

  3. Qingdao New Energy Shandong Laboratory, Qingdao, China

    Longfei Cui, Shu Zhang, Jiangwei Ju & Guanglei Cui

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

    Longfei Cui & Guanglei Cui

  5. National Synchrotron Radiation Research Center, Hsinchu, Taiwan

    Ting-Shan Chan, Yu-Cheng Huang & Shu-Chih Haw

  6. Department of Electrophysics, National Yang Ming Chiao Tung University (NYCU), Hsinchu, Taiwan, Republic of China

    Jin-Ming Chen

  7. Max Planck Institute for Chemical Physics of Solids, Dresden, Germany

    Zhiwei Hu

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Contributions

G.C. and J.J. proposed the concepts. L.C. designed and carried out the experiments. S.Z. performed the theoretical simulations. L.C., S.Z., T.L., J.X. and J.L. conducted the materials preparation. J.W. conducted the PFG-NMR studies. T.-S.C., Y.-C.H., S.-C.H., J.-M.C. and Z.H. conducted the XAS studies. L.C., Y.W., Y.Z., J.Z., G.X. and J.M. analysed the data. J.J. supervised the research. L.C. wrote the manuscript with the help from G.C. and J.J. All authors discussed the results and commented on the manuscript.

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Correspondence to Jiangwei Ju or Guanglei Cui.

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Cui, L., Zhang, S., Ju, J. et al. A cathode homogenization strategy for enabling long-cycle-life all-solid-state lithium batteries. Nat Energy 9, 1084–1094 (2024). https://doi.org/10.1038/s41560-024-01596-6

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