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All-solid-state batteries (ASSBs) that employ anode-less electrodes have drawn attention from across the battery community because they offer competitive energy densities and a markedly improved cycle life. Nevertheless, the composite matrices of anode-less electrodes impose a substantial barrier for lithium-ion diffusion and inhibit operation at room temperature. To overcome this drawback, here, the conversion reaction of metal fluorides is exploited because metallic nanodomains formed during this reaction induce an alloying reaction with lithium ions for uniform and sustainable lithium (de)plating. Lithium fluoride (LiF), another product of the conversion reaction, prevents the agglomeration of the metallic nanodomains and also protects the electrode from fatal lithium dendrite growth. A systematic analysis identifies silver (I) fluoride (AgF) as the most suitable metal fluoride because the silver nanodomains can accommodate the solid-solution mechanism with a low nucleation overpotential. AgF-based full cells attain reliable cycling at 25 °C even with an exceptionally high areal capacity of 9.7 mAh cm

Sulfide‐based all‐solid‐state batteries (ASSBs) have been featured as promising alternatives to the current lithium‐ion batteries (LIBs) mainly owing to their superior safety. Nevertheless, a solution‐based scalable manufacturing scheme has not yet been established because of the incompatible polarity of the binder, solvent, and sulfide electrolyte during slurry preparation. This dilemma is overcome by subjecting the acrylate (co)polymeric binders to protection−deprotection chemistry. Protection by the tert‐butyl group allows for homogeneous dispersion of the binder in the slurry based on a relatively less polar solvent, with subsequent heat‐treatment during the drying process to cleave the tert‐butyl group. This exposes the polar carboxylic acid groups, which are then able to engage in hydrogen bonding with the active cathode material, high‐nickel layered oxide. Deprotection strengthens the electrode adhesion such that the strength equals that of commercial LIB electrodes, and the key electrochemical performance parameters are improved markedly in both half‐cell and full‐cell settings. The present study highlights the potential of sulfide‐based ASSBs for scalable manufacturing and also provides insights that protection−deprotection chemistry can generally be used for various battery cells that suffer from polarity incompatibility among multiple electrode components.