THE EFFECT OF HSAB PRINCIPLE ON ELECTROCHEMICAL PROPERTIES OF POLYMER-IN-SALT ELECTROLYTES WITH ALIPHATIC POLYMER

Abstract

To obtain high ambient ionic conductivity of solid polymer electrolyte (SPE), we introduce polymer-in-salt system with ion hopping mechanism contrary to traditional salt-in-polymer system with segmental motion mechanism. In polymer-in-salt system, the interaction between polymer and salt is important because polymer-in-salt electrolyte contains a large amount of salt. Thus, we try to solve the origin of interaction between polymer and salt by using hard/soft acid base (HSAB) principle. The SPEs are made up of two types of polymers (poly(ethylene oxide) (PEO, hard base) and poly(ethylene imine) (PEI, softer base than PEO)) and four types of salts ( LiCF 3 SO 3 (hard cation/hard anion), LiCl (hard cation/soft anion), AgCF 3 SO 3 (soft cation/hard anion), and AgCl (soft cation/soft anion)) according to HSAB principle. In salt-in-polymer system, ionic conductivities of SPEs were affected by HSAB principle but in polymer-in-salt system, they were influenced by the ion hopping property of salt rather than the solubility of polymer for salt according to HSAB principle. The highest ionic conductivities of PEO-based and PEI-based SPEs were 5.13 × 10-4Scm-1 and 7.32 × 10-4Scm-1 in polymer-in-salt system, respectively.