Electrostatic Potential Guided Design of Multi‐Hydrogen Bond Polymer Electrolytes for Anion/Cation Redistribution

Abstract Due to the complexity of polymer electrolytes with dual‐ion adsorption sites for cations and anions, their impacts on solvation structure and interface evolution‐critical factors for long‐term cycle performance of cells‐remain unclear. Herein, a concept of dual‐ion redistribution has been proposed to achieve the optimal distribution of cations and anions within solvation sheath and at the interface. As a proof of concept, the electrostatic potential (ESP) is employed as a descriptor to screen 2‐(3‐(6‐methyl‐4‐oxo‐1,4‐dihydropyrimidin‐2‐yl) ureido) ethyl methacrylate (UPyMA) monomers with the highest degree of charge delocalization for the preparation of the multi‐hydrogen bond polymer electrolyte (MHBPE). In the bulk, the pronounced interaction of [Li + ···polymer] and the hydrogen bond enrichment effect induce the formation of anion‐rich solvation structures. At the interface, anion shielding protection causes priority sacrifices of anions at the lithium metal anode, reducing the side reactions. Impressively, LiNi 0.6 Co 0.2 Mn 0.2 O 2 ||MHBPE||Li achieves a remarkable cycling stability with high‐capacity retention of 81.39% after 1500 cycles. In addition, MHBPE with a cathode area loading of 6.52 mg cm −2 delivers an excellent capacity retention of 91.7% at 300 cycles. This work provides a new guideline for the improvement of solvation structure and optimization of interface in the electrolytes with dual‐ion adsorption sites.