Polysiloxane-based Electrolytes: Influence of Salt Type and Polymer Chain Length on the Physical and Electrochemical...

An oligo/poly(methyl(2-(tris(2-H methoxyethoxy)silyl)ethyl)siloxane)), 390EO, and 2550EO, were synthesized. Dilute electrolyte solutions of 390EO and 2550EO were prepared using LiTFSI, LiFSI, and LiPF₆ . The influence of the length of the siloxane polymer chain, salt type, and Si-tripodand centers at the side chain on ionic conductivity, t_Li ⁺ , and physical properties were examined. Both electrolyte systems showed high values of t_Li ⁺ (0.35 for 2550EO/LiTFSI and 0.64 for 390EO/LiTFSI). Alternatively 390EO/LiPF₆ and 2550EO/LiPF₆ displayed high t_Li ⁺ values of 0.61 and 0.44, respectively, while 390EO/LiFSI displayed the smallest t_Li+ (0.25). To clarify the role played by the Li⁺ environment in Li⁺ transport, the solvation states of electrolytes were examined. It was observed that anion solvation can be achieved using siloxane-based solvent in all systems. Walden plot analysis demonstrates that ionic diffusion was not controlled by either macroviscosity/microviscosity in the siloxane-based polymer electrolytes. Ions instead move along a relatively smooth ion-pathway without complete full segmental reorientation in 2550EO as a result of decoupling and high ion solvation behavior. Conversely, in 390EO, ions might move to available sites by a jumping after decoupling with low ion solvation behavior. Consequently, a high t _Li ⁺ was achieved, and the oxidative stability of the salt was ensured.