All-solid-state lithium-sulfur batteries (ASLSBs) have been attracting attention as next-generation batteries because of their high theoretical energy density, which exceeds that of traditional lithium-ion batteries. However, the performance of ASLSBs is limited by the sluggish redox reaction kinetics of lithium sulfide (Li₂S) and S₈ cathodes and the electrochemical degradation of cathode materials and solid electrolytes during cycling. Herein, we report a cathode design consisting of Li₂S and transition-metal sulfides. This cathode design enhances the redox reaction kinetics of the cathode and suppresses interfacial degradation between the cathodes and solid electrolytes in the composite cathodes. The interface design uses titanium disulfide, molybdenum sulfide (MoS₂), and tungsten sulfide to facilitate redox reaction kinetics, which improves the practical performance of ASLSBs. Among the composite cathodes examined in this work, the Li₂S-MoS₂ composite cathode exhibited the highest discharge capacity of 661 mA h g^-1 (2.09 mA h cm^-2) after 100 cycles. Electrochemical impedance analysis demonstrated that transition-metal sulfides, particularly MoS₂, suppressed the increase in resistance through cycling of the composite cathodes. This finding suggests that transition-metal sulfides in Li₂S composite cathodes multifunction as redox mediators and buffer layers, improving practical battery performance. Therefore, the electrode design offered in this study enhances the electrochemical utilization and long-term stability of ASLSBs.

Li₁₀GeP₂S₁₂ solid electrolytes for all-solid-state batteries were synthesised rapidly through liquid-phase method in 7.5 h.

Solution processing technology for the manufacturing of all‐solid‐state batteries (ASSBs) holds great promise of scalability and low cost over ball milling and solid‐state methods. However, conventional liquid‐phase synthesis for solid electrolytes has yet to translate into large‐scale manufacturing to address commercialization challenges. Herein, solution processing via dynamic sulfide radical anions is developed, providing rapid and scalable manufacturing of Li₇P₃S₁₁ solid electrolytes (SEs). A mixture of Li₂S, P₂S₅, and excess elemental sulfur in a mixed solvent of acetonitrile, tetrahydrofuran, and ethanol forms a homogenous precursor solution containing the S₃ ^·− radical anion. The presence of ethanol enhances the chemical stability of S₃ ^·−. The resulting sulfide radical anions serve as a mediator with two strategies: the soluble polysulfide formation and activation of P₂S₅, and thus allows the generation of the precursor solution in 2 min. The Li₇P₃S₁₁ is prepared in 2 h without the need for ball milling or high‐energy treatment, which shows higher ionic conductivity (1.2 mS cm⁻¹ at 25 °C) and excellent cell performance of ASSBs cells than Li₇P₃S₁₁ prepared by ball milling. The solution processing technology reported here paves the way for the accelerated adoption of practical ASSBs manufacturing.