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Ether-based polymer electrolytes are limited by their sluggish Li + transport kinetics and narrow electrochemical stability windows. Herein, a new P(DOX-MA) polymer electrolyte with anion-dominated solvation structure is rationally designed, which is controllably synthesized via in-situ cationic ring-opening polymerization of 1,3-dioxane (DOX) and 3-methylglutaric anhydride (MA). By integrating weakly coordinated Li-O(ester) groups and sterically hindered methyl (-CH 3 ) substituents into the P(DOX-MA) polymer backbone, the interaction between Li + and polymer is regulated. As a result, an anion-rich solvation structure is constructed in the resulting polymer electrolyte. This strategy effectively addresses the key challenges of Li + transport kinetics and electrochemical stability in polymer electrolytes. The P(DOX-MA) electrolyte delivers high Li + transference number (0.83), wide electrochemical stability window (4.98 V) and good interfacial stability. Experimental and theoretical results reveal that P(DOX-MA) electrolyte facilitates the formation of robust inorganic-rich solid electrolyte interphase (SEI) and effectively suppresses dendrite growth. As a result, the Li||Li symmetric cell achieves stable cycling for over 2000 h at 0.5 mA cm −2 , meanwhile, the Li||LiFePO 4 cells show excellent cycling stability at room temperature. This work not only elucidates the intrinsic correlations among polymer structure, solvation behavior and interfacial chemistry, but also offers a feasible and scalable design strategy for next-generation polymer electrolytes.
Wang et al. (Tue,) studied this question.