Scalable preparation of asymmetrical bilayer sulfide/halide electrolyte membranes for all-solid-state batteries with high voltage

All-solid-state batteries (ASSBs) are considered to be the most promising candidates for improving battery safety and energy density. Sulfide electrolytes have a narrow electrochemical window, which hinders their applications coupled with high-voltage cathodes. Halide electrolytes with high-voltage endurance can help solve this problem. Herein, the combination of spraying and slurry-coating methods was adopted as a practical route to process a free-standing Li6PS5Cl (LPSCl) asymmetrical electrolyte membrane (19.23 Omega cm2, 75 mu m) decorated with a 10 mu m Li3InCl6 (LICl) layer. The LICl-LPSCl asymmetrical electrolyte membranes enhanced the high-voltage stabilities to match those of LiNi0.83Co0.11Mn0.06O2 (NCM811) and Li1.2Ni0.13Co0.13Mn0.54O2 (LRMO) cathodes. The NCM811 divided by LICl-LPSCl divided by nSi ASSB achieved an initial coulombic efficiency (ICE) of 85.13% and a capacity retention of 77.16% after 200 cycles. Compared with the LPSCl membrane, the LICl-LPSCl membrane displayed high stability with the LRMO cathode as the charging cut-off voltage increased to 4.7 V, which improved the initial charge capacity from 143 to 270 mAh g-1 and achieved stable cycling of 160 mAh g-1 at 0.5 C. Additionally, we attempted continuous LICl-LPSCl membrane production and utilized the product to fabricate a pouch-type ASSB based on LRMO. The fabrication of the LICl-LPSCl electrolyte membrane demonstrated its potential for controllable and industry-adaptable applications in ASSBs.