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High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes

Abstract

All-solid-state Li batteries (ASSBs) employing inorganic solid electrolytes offer improved safety and are exciting candidates for next-generation energy storage. Herein, we report a family of lithium mixed-metal chlorospinels, Li2InxSc0.666−xCl4 (0 ≤ x ≤ 0.666), with high ionic conductivity (up to 2.0 mS cm−1) owing to a highly disordered Li-ion distribution, and low electronic conductivity (4.7 × 10−10 S cm−1), which are implemented for high-performance ASSBs. Owing to the excellent interfacial stability of the SE against uncoated high-voltage cathode materials, ASSBs utilizing LiCoO2 or LiNi0.85Co0.1Mn0.05O2 exhibit superior rate capability and long-term cycling (up to 4.8 V versus Li+/Li) compared to state-of-the-art ASSBs. In particular, the ASSB with LiNi0.85Co0.1Mn0.05O2 exhibits a long life of >3,000 cycles with 80% capacity retention at room temperature. High cathode loadings are also demonstrated in ASSBs with stable capacity retention of >4 mAh cm−2 (~190 mAh g−1).

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Fig. 1: X-ray diffraction patterns and Li-ion conductivity of Li2InxSc0.666−xCl4.
Fig. 2: Structure of Li2In1/3Sc1/3Cl4 and proposed Li-ion diffusion pathway.
Fig. 3: Room temperature rate capability of ASSBs.
Fig. 4: Long-term and high-voltage electrochemical performance of ASSBs.
Fig. 5: High-loading ASSB electrochemical performance.
Fig. 6: ASSB cell impedance evolution during cycling at a C/5 rate.
Fig. 7: Interface evolution between NCM85 and Li2In1/3Sc1/3Cl4 at high voltage up to 4.8 V versus Li+/Li.
Fig. 8: Ionic and electronic percolation within cathode composite.

Data availability

Data generated and analysed in this study are included in the paper and Supplementary Information. The single-crystal X-ray crystallographic data for the structure reported in this study has been deposited at the Cambridge Crystallographic Data Centre under deposition number 2115525. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk.

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Acknowledgements

This work was supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences and NSERC via their Canada Research Chair and Discovery Grant programmes. The neutron diffraction measurement at the POWGEN instrument at Oak Ridge National Laboratory, Spallation Neutron Source, was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. TOF-SIMS measurements were performed at the Justus Liebig University Giessen (funding through Bundesministerium für Bildung und Forschung projects 03XP0177D/03XP0228C). We thank BASF SE for providing NCM622 and NCM85 cathode active materials.

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L.Z. and L.F.N. conceived and designed the experimental work. L.Z. performed the synthesis of the solid electrolytes, powder X-ray diffraction measurements, structural resolution of powder neutron diffraction and the electrochemistry of all-solid-state batteries. T.-T.Z. performed the TOF-SIMS measurements, and data analysis was performed by T.T.Z. and J.J. C.Y.K. performed the SEM measurements. S.Y.K. performed the electrochemistry of liquid NCM cells. A.A. performed single-crystal diffraction and structure resolution. Q.Z. performed the powder neutron diffraction measurements. L.Z. and L.F.N. wrote the manuscript with input from all authors.

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Correspondence to Linda F. Nazar.

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Peer review information Nature Energy thanks Yoon Seok Jung and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–28, Notes 1–6 and Tables 1–8.

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Zhou, L., Zuo, TT., Kwok, C.Y. et al. High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes. Nat Energy 7, 83–93 (2022). https://doi.org/10.1038/s41560-021-00952-0

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