Integrated Configuration Design Strategy Via Cathode‐Gel Electrolyte With Forged Solid Electrolyte Interface Toward Advanced Lithium‐Sulfurized Polyacrylonitrile Batteries

Abstract Li‐SPAN batteries are a promising energy storage system, providing remarkable energy density and high Coulomb efficiency. However, the inherent sluggishness of the cathode's electrochemical kinetics and the instability of the Li anode hamper their cycle lifespan. In this study, a novel design of integrated configuration between cathode and electrolyte that addresses the challenges and promises to reshape the landscape of Li‐SPAN, significantly enhancing the cycling stability, is presented. An artificial solid electrolyte interface (ASEI) is forged to simultaneously stabilize the Li anode and improve the interfacial compatibility, enabling an all‐in‐one battery system. A vertically aligned cathode structure is achieved using directional ice templating, enabling efficient Li‐ion diffusion and enhancing electrochemical kinetics. The Li metal anode is coated with a MOF‐on‐COF ASEI, ensuring uniform Li + deposition and high Li‐ion transference number (0.86). Dual surface engineering further enhances the Li‐SPAN cell, exhibiting a low capacity decay rate of 0.037% per cycle after 1000 cycles and superior C‐rate performance. This study introduces promising strategies for effectively overcoming the challenges associated with the SPAN cathode and Li anode and paves the way for the design of high‐performance Li‐SPAN batteries, unlocking their full potential in the field of advanced energy storage systems.