Novel PEO-based composite solid polymer electrolytes incorporated with active inorganic–organic hybrid polyphosphazene microspheres

Inorganic–organic hybrid poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres with active hydroxyl groups were incorporated in poly(ethylene oxide) (PEO), using LiClO4 as a dopant salt, to form a novel composite polymer electrolyte (CPE). The polymer chain flexibility and crystallinity properties are studied by DSC. The effects of active PZS microspheres on the electrochemical properties of the PEO-based electrolytes, such as ionic conductivity, lithium ion transference number, and electrochemical stability window are studied by electrochemical impedance spectroscopy and steady-state current method. Maximum ionic conductivity values of 3.36 × 10−5 S cm−1 at ambient temperature and 1.35 × 10−3 S cm−1 at 80 °C with 10 wt.% content of active PZS microspheres were obtained and the lithium ion transference number was 0.34. The experiment results showed that the inorganic–organic hybrid polyphosphazene microspheres with active hydroxyl groups can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolytes more effectively comparing with traditional ceramic fillers such as SiO2.