Interphase Stabilization of LiNi0.5Mn1.5O4 Cathode for 5 V‐Class All‐Solid‐State Batteries

Employing high voltage cobalt-free spinel LiNi_0.5 Mn_1.5 O₄ (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li₆ PS₅ Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li₃ InCl₆ ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li₃ PO₄ protective layer coating, LNMO with Li₃ InCl₆ displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. This work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.