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High-energy all-solid-state lithium batteries enabled by Co-free LiNiO2 cathodes with robust outside-in structures

Nature Nanotechnology volume 19, pages 208–218 (2024)Cite this article

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Abstract

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O2 synthesis and subsequent atomic layer deposition of a unique ultrathin LixAlyZnzOδ protective layer comprising a LixAlyZnzOδ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm−2), a high specific cathode capacity (203 mAh g−1), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g−1 at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.

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Fig. 1: Morphological and structural analyses showing the robust outside-in structures of LAZO@LNO.
Fig. 2: Electrochemical behaviour showing the significantly enhanced Li-ion transport dynamics for LAZO@LNO-based ASSLBs.
Fig. 3: X-ray diffraction and PFIB-SEM analysis showing the electro-chemo-mechanical evolution of the composite cathodes at different stages.
Fig. 4: X-ray absorption spectroscopy (XAS) analysis showing the evolution of the LNO, LAZO@LNO and LPSC structure in the composite cathodes at different stages.
Fig. 5: XPS and Raman analysis showing the evolution of the LPSC surface composition in the composite cathodes at different stages.
Fig. 6: Superior electrochemical performance of LAZO@LNO- over LNO-based ASSLBs.

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All the data generated and analysed in this study are included in the paper and Supplementary Information. The data that support the plots within this paper are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the US–Israel Energy Center programme managed by the US–Israel Binational Industrial Research and Development (BIRD) Foundation. In addition, the project is supported by Champion Motors Ltd, the Science and Engineering Research Board for Ramanujan fellowship (RJN/2020/000075, A.M.) and the Ministry of Science and Technology in Taiwan (MOST 110-2112-M-A49-002-MY3, C.-Y.K.). We acknowledge the support from the Max Planck-POSTECH/Hsinchu Center for Complex Phase Materials.

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  1. These authors contributed equally: Longlong Wang, Ayan Mukherjee.

Authors and Affiliations

  1. Department of Chemistry and Bar-Ilan Institute of Nanotechnology and Advanced Materials, Bar-Ilan University, Ramat Gan, Israel

    Longlong Wang, Ayan Mukherjee, Sankalpita Chakrabarty, Reut Yemini, Sri Harsha Akella, Arka Saha, Sarah Taragin, Hagit Aviv, Doron Naveh, Doron Aurbach & Malachi Noked

  2. Department of Materials, University of Oxford, Oxford, UK

    Longlong Wang, Boyang Liu, Xiangwen Gao & Peter G. Bruce

  3. CSIR-Institute of Minerals and Materials Technology, Bhubaneswar, India

    Ayan Mukherjee

  4. National Synchrotron Radiation Research Center, Hsinchu, Taiwan, Republic of China

    Chang-Yang Kuo, Ting-Shan Chan, Hong-Ji Lin, Jyh-Fu Lee & Chien-Te Chen

  5. Department of Electrophysics, National Yang Ming Chiao Tung University, Hsinchu, Taiwan, Republic of China

    Chang-Yang Kuo

  6. Forge Nano Inc, Thornton, CO, USA

    Arrelaine A. Dameron & Jaime W. DuMont

  7. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel

    Daniel Sharon

  8. Department of Chemical Engineering, Indian Institute of Technology Delhi, Delhi, India

    Suddhasatwa Basu

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

    Zhiwei Hu

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Contributions

L.W., A.M. and M.N. conceived the idea. L.W., A.M. and Z.H. synthesized the materials. L.W., A.M. and R.Y. performed the ALD coating. L.W. and A.M. performed the X-ray diffraction, SEM, STEM and electrochemical measurements. L.W., S.C. and B.L. performed the PFIB measurements. C.-Y.K. and Z.H. carried out the XAS measurements and calculations. L.W., S.H.A., H.A. and D.N. performed the operando Raman measurements. L.W., A.S. and S.T. performed the XPS measurements. C.-Y.K., Z.H., T.-S.C., H.-J.L., J.-F.L. and C.-T.C. helped to analyse the XAS data. A.A.D. and J.W.D. performed the cost estimation of the ASSLB production process including ALD. D.S., X.G., S.B. and P.G.B. provided valuable suggestions to improve this project. L.W., M.N. and D.A. wrote the paper with critical inputs from all other authors. All authors edited and approved the manuscript.

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Correspondence to Zhiwei Hu, Doron Aurbach or Malachi Noked.

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Wang, L., Mukherjee, A., Kuo, CY. et al. High-energy all-solid-state lithium batteries enabled by Co-free LiNiO2 cathodes with robust outside-in structures. Nat. Nanotechnol. 19, 208–218 (2024). https://doi.org/10.1038/s41565-023-01519-8

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