The establishment of three-electrode cells for all-solid-state lithium-ion batteries is an important issue to clarify the electrochemical behavior of the battery components and solve problems for the practical applications. Here we prepared an all-solid-state three-electrode cell with a chemically-reduced Li₄Ti₅O₁₂ reference electrode and investigated electrochemical properties of a LiCoO₂ composite electrode in a Li-In|Li₁₀GeP₂S₁₂|LiCoO₂ cell. Plateau potentials in charge-discharge curves were coincident with reported values. Cell impedance measured with two-electrode configuration agreed well with the sum of the impedances of the positive and the negative electrodes measured with the reference electrode. These results show that chemically-reduced Li₄Ti₅O₁₂ reference electrode was worked as a Li₇Ti₅O₁₂|Li₄Ti₅O₁₂ reference electrode and electrochemical properties of the LiCoO₂ electrode and the Li-In electrode were separated. From the temperature and the state of charge dependences of LiCoO₂ impedance, resistances related to interface or interphase and charge-transfer reaction were identified. These results show that all-solid-state cells with chemically-reduced Li₄Ti₅O₁₂ reference electrodes are promising candidates for three-electrode cells for all-solid-state lithium-ion battery systems.

全固态锂离子电池的三电极电池的建立是一个重要的问题，以阐明电池组件的电化学行为并解决实际应用中的问题。在这里，我们制备了具有化学还原的Li ₄ Ti ₅ O ₁₂参比电极的全固态三电极电池，并研究了在Li-In | Li ₁₀ GeP ₂ S ₁₂ | LiCoO中的LiCoO ₂复合电极的电化学性能。₂细胞。充放电曲线中的高原电位与报道的值一致。用两电极配置测量的电池阻抗与用参考电极测量的正极和负极的阻抗之和非常吻合。这些结果表明，将化学还原的Li ₄ Ti ₅ O ₁₂参比电极用作Li ₇ Ti ₅ O ₁₂ | Li ₄ Ti ₅ O ₁₂参比电极，并且分离了LiCoO ₂电极和Li-In电极的电化学性质。。从温度和电荷状态对LiCoO _2的依赖性阻抗，与界面或相间和电荷转移反应有关的电阻被确定。这些结果表明，具有化学还原的Li ₄ Ti ₅ O ₁₂参比电极的全固态电池有望成为全固态锂离子电池系统三电极电池的候选材料。