Effect of Chemical Structure and Salt Concentration on the Crystallization and Ionic Conductivity of Aliphatic Polyethers

Poly(ethylene oxide) (PEO) is the most widely used polymer in the field of solid polymer electrolytes for batteries. It is well known that the crystallinity of polymer electrolytes strongly affects the ionic conductivity and its electrochemical performance. Nowadays, alternatives to PEO are actively researched in the battery community, showing higher ionic conductivity, electrochemical window, or working temperature range. In this work, we investigated polymer electrolytes based on aliphatic polyethers with a number of methylene units ranging from 2 to 12. Thus, the effect of the lithium bis(trifluoromethanesulfone) imide (LiTFSI) concentration on the crystallization behavior of the new aliphatic polyethers and their ionic conductivity was investigated. In all the cases, the degree of crystallinity and the overall crystallization rate of the polymers decreased drastically with 30 wt % LiTFSI addition. The salt acted as a low molecular diluent to the polyethers according to the expectation of the Flory–Huggins theory for polymer–diluent mixtures. By fitting our results to this theory, the value of the interaction energy density (B) between the polyether and the LiTFSI was calculated, and we show that the value of B must be small to obtain high ionic conductivity electrolytes.