Molecular Design of Solid Polymer Electrolytes with Enthalpy–Entropy Manipulation for Li Metal Batteries with Aggressive Cathode Chemistry

Solid polymer electrolytes (SPEs) with high ion conductivity, high Li⁺ transference number, and a wide electrochemical window are promising for the next-generation high-energy Li metal batteries (LMBs). Here we describe an enthalpy-entropy manipulation strategy enabling a class of polycarbonate-based copolymeric electrolytes (PCCEs) with regulated cation/anion solvation via a molecular design of the polymer backbone. By integrating a weakly solvating linear carbonate with another strongly solvating cyclic carbonate segment in the polymer backbone, the cation-dipole coordination for Li⁺ ions (with two types of carbonyl groups) is weakened (low enthalpy penalty) and nondirectional (high entropy penalty), which enables a weak solvation and rapid diffusion of Li⁺. We further introduce a bis-acrylamide-based cross-linking segment which, other than imparting high mechanical strength, exhibits dihydrogen bonding with the difluoro(oxalate) borate anions, which is strong (high enthalpy penalty) and directional (low entropy penalty), thus restricting the migration of anions. As a result, the PCCE delivers a high ionic conductivity of 0.66 mS cm^-1 with a high Li⁺ transference number (0.76) at 25 °C, as well as high oxidation stability. By an in situ polymerization approach, the PCCE enables LMBs using high-nikel LiNi_0.8Co_0.1Mn_0.1O₂ cathodes with a high capacity retention of 82.2% over 800 cycles with a cutoff voltage of 4.5 V and further LMBs using aggressive LiNi_0.5Mn_1.5O₄ cathodes with a 96.4% capacity retention over 300 cycles with a cutoff voltage of 5.0 V. The described enthalpy-entropy manipulation approach offers a unique perspective for the molecular design of high-performance SPEs for high-energy Li metal batteries.