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In situ X-ray photoelectron spectroscopy investigation of the solid electrolyte interphase in a Li/Li6.4Ga0.2La3Zr2O12/LiFePO4 all-solid-state battery

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Abstract

The fundamental understanding of the solid electrolyte/electrode interphase during charge and discharge is promising for the development of all-solid-state batteries. Here, we employ a solid-state Li/Li6.4Ga0.2La3Zr2O12/LiFePO4 cell and study in situ the electrolyte/anode and electrolyte/cathode interphase as a function of applied potential under ultra-high vacuum using X-ray photoelectron spectroscopy. An ultra-thin interfacial passivation layer is formed at the Li/Ga-doped LLZO interphase, which inhibits the Ga-LLZO from being further reduced by Li. During charging, the oxidation reaction of Li with Ga-LLZO still occurs, which is evidenced by the broadening of the full width at half maximum (FWHM) and shifting of the Li 1s peak towards lower binding energies and the increment of Li2O peak intensity in the O 1s range. The Ga-LLZO solid electrolyte/LiFePO4 cathode interphase was also studied by in situ XPS under UHV. The deintercalation of Li+ ion is evidenced by the broadening and shifting of Fe 2p peak during charging. Other components shift by the same values as the applied potential. These results indicate good reversibility of the LiFePO4/Ga-LLZO interphase upon charge/discharge. The long-term stability of the LiFePO4/Ga-LLZO interphase was also examined during charging/discharging for 100 cycles. These insights provide a new perspective for understanding of the solid electrolyte interphase, which enables high energy density, long-term stability, and safety for next-generation batteries.

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Acknowledgments

We would like to thank a joint project funded by National Natural Science Foundation of China (NSFC) and Deutsche Forschungsgemeinschaft (DFG) (EN 370/28-1) and the National Natural Science Foundation of China (No.51761135123).

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Authors and Affiliations

  1. Institute of Electrochemistry, Clausthal University of Technology, Arnold-Sommerfeld-Strasse 6, 38678, Clausthal-Zellerfeld, Germany

    Zhen Liu, Guozhu Li, Andriy Borodin & Frank Endres

  2. School of Material Science and Engineering, Shanxi University of Science and Technology, 710021, Xi’an, China

    Xiaoxu Liu

  3. Center for Composite Materials and Structure, Harbin Institute of Technology, Harbin, China

    Yao Li

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  1. Zhen Liu
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  2. Guozhu Li
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Liu, Z., Li, G., Borodin, A. et al. In situ X-ray photoelectron spectroscopy investigation of the solid electrolyte interphase in a Li/Li6.4Ga0.2La3Zr2O12/LiFePO4 all-solid-state battery. J Solid State Electrochem 23, 2107–2117 (2019). https://doi.org/10.1007/s10008-019-04296-4

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  • DOI: https://doi.org/10.1007/s10008-019-04296-4

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