ABSTRACT All‐solid‐state lithium‐ion batteries (ASSLIBs) have emerged as a new generation of energy storage systems, owing to their high energy density and safety advantages. However, their extensive application is hindered by both the insufficient ionic conductivity of solid electrolytes and the interfacial mismatch between electrolytes and electrodes. To address this issue, we developed glassy ASSLIBs by harmoniously coupling glass‐ceramic electrolytes with vanadium phosphoborate glass electrodes. The electrolytes were prepared from an aluminophosphate glass system through controlled crystallization. The optimized electrolyte exhibited a high ionic conductivity (1.15 × 10 − 4 S cm − 1 ) and a low activation energy (0.23 eV) for Li + diffusion. The interfacial compatibility between the glass electrode and the glass‐ceramic electrolyte enabled fast electron/ion transport in an assembled full cell (with a Li metal anode). The derived glassy battery delivered an initial discharge capacity of 907 mA h g − 1 at 0.1 A g − 1 and a capacity of 228 mA h g − 1 after 500 cycles, along with superior rate performance. Thus, this study offers a promising strategy for advancing ASSLIBs.
Zheng et al. (2026) studied this question.