Effects of Molecular Weight on the Electrochemical Properties of Poly(vinylidene difluoride)-Based Polymer Electrolytes

Polymer-based electrolytes have attracted ever-increasing attention for solid-state batteries due to their excellent flexibility and processability. Among them, poly(vinylidene difluoride) (PVDF)-based electrolytes with high ionic conductivity, wide electrochemical stability window, and good mechanical properties show great potential and have been widely investigated by using different Li salts, solvents, and inorganic fillers. Here, we report the influence of the molecular weight of PVDF itself on the electrochemical properties of the electrolytes by using two kinds of common PVDF polymers, i.e., PVDF 761 and 5130. Our results demonstrate that the electrolyte with a larger molecular weight (PVDF 5130) has a denser structure and lower crystallinity, and thus much better electrochemical performance, than one with a smaller molecular weight (PVDF 761). With PVDF 5130, the LiFePO₄-based solid-state cells present a steady cycling performance with a capacity retention of 85% after 1000 cycles at 1 C and 30 °C. The cycle life of the LiCoO₂-based solid-state cells is also extended by using PVDF 5130.