Effect of network homogeneity on mechanical, thermal and electrochemical properties of solid polymer electrolytes prepared by homogeneous 4-arm poly(ethylene glycols).

Mechanically tough solid polymer electrolytes (SPEs) are required to meet the demand for flexible and stretchable electrochemical devices for diverse applications, especially for wearable devices. It is well known that the inhomogeneity of a polymer network greatly affects its mechanical properties, but the evaluation of its effect on electrolyte properties including mechanical properties has not been accomplished yet because of the coexistence of various inhomogeneities (e.g., dangling bonds, loops, chain entanglements, and inhomogeneous distribution of cross-linking points). Herein, we discuss the effect of distribution of cross-linking densities in SPEs on its electrolyte properties by employing a model polymer network composed of a homogeneous 4-arm poly(ethylene glycol) (tetra-PEG) network and Li[TFSA] ([TFSA]: bis(trifluoromethanesulfonyl)amide). Tetra-PEGs having different molecular weights (Mn = 5, 10, 20, and 40 kDa) are subjected to the Michael addition reaction to induce network inhomogeneity while the average cross-linking densities are matched. It was found that thermal and ion transport properties of tetra-PEG SPEs do not depend on network inhomogeneity but on the average network size, which indicates that these properties reflect the averaged thermal fluctuation of polymer chains in terms of spatial and temporal dimensions. On the other hand, the mechanical toughness was largely dependent on the network homogeneity, and fracture strain, energy, and Young's modulus decreased by introducing network inhomogeneity. Rheological measurements showed that a transient cross-linking between Li cations and oxygens of tetra-PEG as well as the homogeneous distribution of the chemical cross-linking points contribute to the excellent mechanical properties of SPEs.