Polymer‐Assisted Silver Coating for Chemically Stable and Dendrite‐Free Interfaces in Sulfide‐Based Anodeless All‐Solid‐State Batteries

ABSTRACT Anodeless all‐solid‐state batteries (ALASSBs) represent a transformative energy storage technology with the potential to maximize energy density and improve safety. The strategic incorporation of lithiophilic materials such as silver and magnesium has recently shown remarkable enhancements in cycling performance, particularly in sulfide‐based ALASSBs. Here, we report a solution‐assisted strategy employing poly(ethylene‐co‐maleic anhydride) (PEMA) to fabricate an ultrathin (∼120 nm) layer containing uniformly dispersed silver nanoparticles (10–20 nm), derived from silver nitrate (AgNO ₃ , ANO), on a copper current collector, denoted as ANO_PEMA@Cu. PEMA simultaneously facilitated controlled silver nucleation and enhanced cohesion, leading to the formation of chemically and electrochemically stable interface with solid electrolyte (Li ₆ PS ₅ Cl). The ANO_PEMA@Cu promoted highly uniform lithium plating/stripping and effectively suppressed lithium dendrite growth, thereby ensuring interfacial stability. The anodeless all‐solid‐state cell incorporating ANO_PEMA@Cu, solid electrolyte, and composite LiNi _0.82 Co _0.10 Mn _0.08 O ₂ (NCM) cathode with an areal capacity of 3.0 mAh cm ⁻² exhibited excellent cycling stability, retaining 80.6% of its initial capacity after 300 cycles at 0.33 C and 30°C without short‐circuiting.