Kinetics of Interfacial Lithium-ion Transfer between a Graphite Negative Electrode and a Li₂S-P₂S₅ Glassy Solid Electrolyte

All-solid-state lithium-ion batteries that use sulfide solid electrolytes have attracted much attention due to their high safety and wide electrochemical window. In this study, highly oriented pyrolytic graphite (HOPG) and 75Li₂S-25P₂S₅ (mol%) glass were used as a model graphite negative electrode and a sulfide solid electrolyte, respectively. Interfacial lithium-ion transfer between 75Li₂S-25P₂S₅ glass and the HOPG electrode was studied by AC impedance spectroscopy measurements. The activation energy of the interfacial lithium-ion transfer was estimated to be around 37 kJ mol⁻¹, which was much smaller than that at the interface between organic liquid electrolytes and HOPG electrode, indicating that the lithium-ion transfer at the interface between 75Li₂S-25P₂S₅ glass and HOPG electrode proceeded quite rapidly. Furthermore, surface deposition of TiO₂ and surface oxidation on HOPG electrodes were performed using the atomic layer deposition (ALD) method. Interfacial lithium-ion transfer between 75Li₂S-25P₂S₅ glass and ALD-modified-HOPG electrodes was also investigated. The activation energies of the interfacial lithium-ion transfer were slightly higher than that of HOPG, but the resistance of the charge-transfer process was lower, indicating that the affinity of the HOPG electrode for the glass electrolyte was improved by surface modification