Understanding Polymerized Ionic Liquids as Solid Polymer Electrolytes for Sodium Batteries.

Solid polymer electrolytes (SPEs) have emerged as promising candidates for sodium-based batteries due to their cost-effectiveness and excellent flexibility. However, achieving high ionic conductivity and desirable mechanical properties in SPEs remains a challenge. In this study, we investigated an AB diblock copolymer, PS-PEA(BuImTFSI), as a potential SPE for sodium batteries. We explored binary and ternary electrolyte systems by combining the polymer with salt and [C3mpyr][FSI] ionic liquid (IL) and analyzed their thermal and electrochemical properties. Differential scanning calorimetry revealed phase separation in the polymer systems. The addition of salt exhibited a plasticizing effect localized to the polyionic liquid (PIL) phase, resulting in an increased ionic conductivity in the binary electrolytes. Introducing the IL further enhanced the plasticizing effect, elevating the ionic conductivity in the ternary system. Spectroscopic analysis, for the first time, revealed that the incorporation of NaFSI and IL influences the conformation of TFSI- and weakens the interaction between TFSI- and the polymer. This establishes correlations between anions and Na+, ultimately enhancing the diffusivity of Na ions. The electrochemical properties of an optimized SPE in Na/Na symmetrical cells were investigated, showcasing stable Na plating/stripping at high current densities up to 0.7 mA cm-2, maintaining its integrity at 70 °C. Furthermore, we evaluated the performance of a Na|NaFePO4 cell cycled at different rates (C/10 and C/5) and temperatures (50 and 70 °C), revealing remarkable high-capacity retention and Coulombic efficiency. This study highlights the potential of solvent-free diblock copolymer electrolytes for high-performance sodium-based energy storage systems, contributing to advanced electrolyte materials.

Impact of optimised quasi-block structures on the properties of polymer electrolytes.

A set of ionic quasi-block copolymers were investigated to determine the effects of their composition and structure on their performance in their application as solid-state battery electrolytes. Diffusion and electrochemical tests have shown that these new quasi-block electrolytes have comparable performance to traditional block copolymers reaching ionic conductivities of 3.8 × 10-4 S cm-1 and lithium-ion diffusion of 4.6 × 10-12 m2 s-1 at 80 °C. It was illustrated that the mechanical properties of each quasi-block electrolyte are highly dependent on the order of monomer addition in polymer synthesis while the phase morphology hints at each of the quasi-blocks' unique compositional make up.