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Ionic conductivity of the LiOH-Li2SO4 system and fabrication of all-solid-state lithium batteries

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Abstract

The solid electrolytes with a low melting temperature are promising for the all-solid-state lithium batteries because such electrolytes enable the battery fabrication without high-temperature sintering (for example, ~ 1000 °C for oxide materials). In this study, a series of LiOH-Li2SO4 systems with different LiOH/Li2SO4 ratios is fabricated by melting LiOH and Li2SO4 at 430 °C, and their ion conduction properties are investigated. The stoichiometric compounds are obtained in 2.2LiOH‧Li2SO4 without segregation of LiOH and Li2SO4, which is rather different from the previously known composition (3LiOH‧Li2SO4). The deviation from this LiOH/Li2SO4 fraction results in a segregation of LiOH or Li2SO4. The conductivities of 2.2LiOH‧Li2SO4 with 5 mol% of Li3BO3 are 1.9 × 10−6 and 6.0 × 10−3 S/cm at 25 and 150 °C, respectively. The all-solid-state batteries are fabricated by hot pressing the solid electrolyte with Li(Ni0.3Co0.6Mn0.1)O2 (cathode) and graphite (anode) at 250 °C under 150 MPa. The contacts of the solid electrolyte with Li(Ni0.3Co0.6Mn0.1)O2 and graphite are intimate, and the by-products are not found at the interphase. The discharge capacities of 80 mAh/g are obtained for 100 cycles at 150 °C when the charging voltage is restricted to 3.95 V. The results of cyclic voltammetry measurement indicate the reductive decomposition of the solid electrolyte at 2.3 and 1.6 V. These reduction currents are decreased with cycling, suggesting the passivation of the anode interphase. On the other hand, the oxidation current is observed above 3.6 V which is not terminated during voltage cycling. In the battery fabrication process, high-temperature sintering is not necessary, and the dense contacts with electrode materials can be made by hot pressing at 250 °C. Furthermore, the batteries are constructed in a dry room where the dew point is maintained at − 40 °C. The present results suggest the potential of the LiOH-Li2SO4 as the solid electrolyte for all-solid-state lithium batteries.

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Acknowledgements

This work was supported by the NGK Environment Innovation Laboratory.

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Authors and Affiliations

  1. Department of Physical Science and Engineering, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya, 466-8555, Japan

    Reona Miyazaki

  2. NGK INSULATORS, LTD, 2-56 Suda-Cho, Mizuho, Nagoya, 467-8530, Japan

    En Yagi, Satoshi Ozaki, Yusaku Suto, Harunobu Onishi, Yosuke Sato, Toshihiro Yoshida & Yuji Katsuda

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  1. Reona Miyazaki
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Correspondence to Reona Miyazaki.

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Miyazaki, R., Yagi, E., Ozaki, S. et al. Ionic conductivity of the LiOH-Li2SO4 system and fabrication of all-solid-state lithium batteries. J Solid State Electrochem 28, 103–111 (2024). https://doi.org/10.1007/s10008-023-05656-x

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