LiI-Doped Sulfide Solid Electrolyte: Enabling a High-Capacity Slurry-Cast Electrode by Low-Temperature Post-Sintering for Practical All-Solid-State Lithium Batteries

All-solid-state lithium batteries (ASSLBs) based on sulfide solid electrolytes (SEs) have received great attention because of the high ionic conductivity of the SEs, intrinsic thermal safety, and higher energy density achievable with a Li metal anode. However, studies on practical slurry-cast composite electrodes show an extremely limited battery performance than the binder-free pelletized electrodes because of the poor interfacial robustness between the active materials and SEs by the presence of a polymeric binder. Here, we employ a low-temperature post-sintering process for the slurry-cast composite electrodes in order to overcome the binder-induced detrimental effects on the electrochemical performance. The LiI-doped Li3PS4 SEs are chosen because the addition of iodine not only improves the Li-ion conductivity and Li metal compatibility but also lowers the glass-transition and crystallization temperatures. Low-temperature post-sintering of composite cathodes consisting of a LiNi0.6Co0.2Mn0.2O2-active material, LiI-doped Li3PS4 SE, polymeric binder, and conducting agent shows a significantly improved electrochemical performance as compared to a conventional slurry-cast electrode containing pre-annealed SEs. Detailed analyses by electrochemical impedance spectroscopy and galvanostatic intermittent titration technique confirm that post-sintering effectively reduces the interfacial resistance and enhances the chemomechanical robustness at solid-solid interfaces, which enables the development of practical slurry-cast ASSLBs with sulfide SEs.