Impact of Li3BO3 Addition on Solid Electrode-Solid Electrolyte Interface in All-Solid-State Batteries

All-solid-state lithium-ion batteries raise the issue of high resistance at the interface between solid electrolyte and electrode materials that needs to be addressed. The article investigates the effect of a low-melting Li₃BO₃ additive introduced into LiCoO₂- and Li₄Ti₅O₁₂-based composite electrodes on the interface resistance with a Li₇La₃Zr₂O₁₂ solid electrolyte. According to DSC analysis, interaction in the studied mixtures with Li₃BO₃ begins at 768 and 725 °C for LiCoO₂ and Li₄Ti₅O₁₂, respectively. The resistance of half-cells with different contents of Li₃BO₃ additive after heating at 700 and 720 °C was studied by impedance spectroscopy in the temperature range of 25–340 °C. It was established that the introduction of 5 wt% Li₃BO₃ into LiCoO₂ and heat treatment at 720 °C led to the greatest decrease in the interface resistance from 260 to 40 Ω cm² at 300 °C in comparison with pure LiCoO₂. An SEM study demonstrated that the addition of the low-melting component to electrode mass gave better contact with ceramics. It was shown that an increase in the annealing temperature of unmodified cells with Li₄Ti₅O₁₂ led to a decrease in the interface resistance. It was found that the interface resistance between composite anodes and solid electrolyte had lower values compared to Li₄Ti₅O₁₂|Li₇La₃Zr₂O₁₂ half-cells. It was established that the resistance of cells with the Li₄Ti₅O₁₂/Li₃BO₃ composite anode annealed at 720 °C decreased from 97.2 (x = 0) to 7.0 kΩ cm² (x = 5 wt% Li₃BO₃) at 150 °C.