Ultra‐Stretchable, Ionic Conducting, Pressure‐Sensitive Adhesive with Dual Role for Stable Li‐Metal Batteries

Abstract The practical application of lithium (Li) metal battery is impeded by the Li dendrite growth and unstable solid electrolyte interphase (SEI) layer. Herein, an ultra‐stretchable and ionic conducting chemically crosslinked pressure‐sensitive adhesive (cPSA) synthesized via the copolymerization of 2‐ethylhexyl acrylate and acrylic acid with poly(ethyleneglycol)dimethacrylate as crosslinker (short for 70cPSA), is developed as both artificial SEI layer and solid polymer electrolyte (SPE) for stable Li‐metal electrode, enabling all‐solid‐state Li metal batteries with excellent cycling performance. As an artificial SEI layer, the 70cPSA‐modified electrodes exhibit excellent electrochemical performance in Li|70cPSA@Cu half cells and 70cPSA@Li|70cPSA@Li symmetric cells. In full cells with LiFePO₄ (LFP) as cathode, the 70cPSA@Li|LFP cell exhibits stable cycling performance over 250 cycles. Utilized as SPE, the all‐solid‐state Li|SPE|LFP cell delivers excellent cycling stability with a capacity retention of 86% over 500 cycles. With high‐voltage LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) as cathode, the Li|SPE|NMC811 cell exhibits a discharge capacity of 124.3 mAh g⁻¹ with a capacity retention of 71% after 200 cycles. The rational design of PSAs and investigation of their dual role for stable and safe Li‐metal batteries may shed a light on adhesive polymers for battery applications.