Diethylenetriaminepentaacetic Acid‐based Conducting Solid Polymer Electrolytes Impede Lithium Dendrites and Impart Antioxidant Capacity in Lithium‐Ion Batteries

Abstract In the development of lithium‐ion batteries (LIBs), cheaper and safer solid polymer electrolytes are expected to replace combustible organic liquid electrolytes to meet the larger market demand. However, low ionic conductivity and inadequate cycling stability impede their commercial viability. Herein, a novel flexible conducting solid polymer electrolytes (CSPEs) based on polyvinyl alcohol (PVA) and ion‐polarized diethylenetriaminepentaacetic acid (P‐DETP) is developed for the first time and applied in LIBs. PVA and P‐DETP form a compact polymer network through hydrogen bonding, enhancing the thermomechanical stability of CSPE while restricting the migration of larger anions. Furthermore, density functional theory calculations confirm that P‐DETP can facilitate the dissociation of Li+‐TFSI‐ via electrostatic attraction, resulting in increased mobility of lithium ions. Additionally, P‐DETP contributes to the formation of a stable electrode‐electrolyte interface layer, effectively suppressing the growth of lithium dendrites and improving antioxidant capacity. These synergistic effects enable CSPE to exhibit remarkable properties including high ionic conductivity (2.8 × 10−4 S cm−1), elevated electrochemical potential (5.1 V), and excellent lithium transference number (0.869). Notably, the P‐DETP/LiTFSI CSPE demonstrates stable performance not only in LiFePO4 batteries but also adapts to high‐nickel ternary LiNi0.88Co0.06Mn0.06O2 cathode, highlighting its immense potential for application in high energy density LIBs.