Comb-shaped single ion conductors based on polyacrylate ethers and lithium alkyl sulfonate

摘要

Comb-shaped single ion conductors have been synthesized by (1) sulfonation of small molecule chloroethyleneglycols, which, after ion exchange to the Li{sup}+ salt were then converted to the acrylate by reaction with acryloyl chloride and copolymerized with polyethylene glycol monomethyl ether acrylate (Mn = 454, n = 8) (PAE{sub}-co-E{sub}3SO{sub}3Li); (2) sulfonation of chloride end groups grafted on to prepolymers of polyacrylate ethers (PAE{sub}8-g-E{sub}nSO{sub}3Li, n = 2, 3). The highest conductivity at 25 ℃ of 2.0 × 10{sup}(-7)Scm{sup}(-1) was obtained for the PAE{sub}8-co-E{sub}3SO{sub}3Li with a salt concentration of EO/Li = 40. The conductivity of PAE8-g-E{sub}3SO{sub}3Li is lower than that of PAE{sub}8-co-E{sub}3SO{sub}3Li at similar salt concentrations, which is related to the incomplete sulfonation of the grafted polymer that leads to a lower concentration of Li{sup}+. The addition of 50wt.% of plasticizer, PC/EMC (1/1, v/v), to PAEg-g-E{sub}2SO{sub}3Li increases the ambient conductivity by three orders of magnitude, which is due to the increased ion mobility in a micro-liquid environment and an increase concentration of free ions as a result of the higher dielectric constant of the solvent. A symmetrical Li/Li cell with an electrolyte membrane consisting of 75 wt.% PC/EMC (1/1, v/v) was cycled at a current density of 100μAcm{sup}(-2) at 85 ℃. The cycling profile showed no concentration polarization after a break-in period during the first few cycles, which was apparently due to reaction of the solvent at the lithium metal surface that reacted with lithium metal to form a stable SEI layer.