Dry-Processable Polymer Electrolytes for Solid Manufactured Batteries

Designing a solid-state electrolyte that satisfies the operating requirements of solid-state batteries is key to solid-state battery applications. The consensus is that solid-state electrolytes need to allow fast ion transport, while providing better interfacial compatibility and mechanical tolerance. Herein, a simple but effective strategy is proposed, combining hard and soft component polymer systems, to exploit a solid polymer electrolyte (SPE) with a 3D network via an in situ graft polymerization. The 3D structure is constructed by a hard cellulose nanocrystal (CNC) as the skeleton and a soft polyacrylonitrile (PAN) as the filler through a dry-processing method. The reported systems have several advantages, including ease of processing, only requiring using an exceedingly small amount of solvent, light weight (ρ = 1.2 g cm^-3), excellent mechanical stability (tensile strength of 9.5 MPa), and high ionic conductivity (3.9 × 10^-4 S cm^-1, 18 °C) and migration number (t_Li = 0.8). In particular, the high conductivity is enabled: the efficient Li⁺ transportation path constructed between CNC-PAN powders and abundant sulfonate radicals and hydroxyl groups on the CNC surface acts as the bridge of Li⁺ transition. When the CNCs are grafted onto the PAN polymer, the dipole-dipole interaction between the nitrile groups of the PAN and the hydroxyl groups of the CNCs can help to improve the mechanical stability and ionic conductivity of the SPE. Moreover, a tightly formed interface between SPE and LiFePO₄ (LFP)/carbon black/SPE cathode can be achieved in an assembled solid-state battery by hot pressing, thus further enhancing the battery's performance.