Understanding Ion Distribution and Diffusion in Solid Polymer Electrolytes

Solid polymer electrolytes (SPEs)-polymer melts with added salts-exhibit ion conduction and high mechanical properties, and are thus promising materials for future energy storage devices. The ion conductivity in an SPE is intricately connected to the salt ion distribution in the polymer matrix. The relationship between ion diffusion and ion distribution in SPEs remains unresolved. Here, we conduct coarse-grained molecular dynamics simulations and establish correlations between ion distribution and transport for a phenomenological SPE model. We propose phase diagrams of SPEs as a function of ion pair size, ion concentration, and the Bjerrum length of the material. A crossover from a discrete ion aggregate to a percolated ion aggregate is demonstrated as a function of ion pair size for low ion concentration in the SPE. The ion diffusion shows a strong correlation with its size, as has been found experimentally. The work provides important design strategies for controlling the ion distribution and enhancing ion conductivity in a polymer matrix.