Self-assembly and energy storage potentials of biphasic phase change azobenzene liquid crystalline block copolymers

Flexible polymeric materials with potentials in energy storage have attracted extensive attention in today's sustainable society. Here, we reported a series of crystalline-liquid crystalline biphasic phase change block copolymers, poly(ethylene oxide)-b-poly(11-(4-(4-cyanophenylazo)phenoxy)undecane methacrylate) (PEO-b-PMAAzo), and studied the UV and Li+ ions coordination-mediated self-assembly for the potentials in phase change energy storage and solid electrolytes. The PEO-b-PMAAzo BCPs possess both the solid-liquid phase transition of PEO and the photo-chemical-thermal energy transition of PMAAzo block. Meanwhile, PEO has the capability to coordinate with the Li+ for the ionic conductivity. We explored the binary phase change behaviors and thermal energy density of the BCPs with different lithium ion concentrations before and after UV irradiation. The addition of LiTFSI salts increases the interaction parameters (chi) of the BCPs leading to phase transition of the self-assembled nanostructures. The phase diagram covering LAM, HEX, GYR, Fddd and HPL nanostructures facilitating ion transport was demonstrated. The PMAAzo block enabled the solid feature of the BCPs and ensured the high energy density and high conductivity. This work demonstrates that the combination of the functional polymers in one BCP not only provides multiple morphology tunabilities but also enables multiple functionalities from energy conversation and storage to ionic conductive electrolytes.