Insight into ion dynamics in a NaClO₄-doped polycaprolactone solid polymer electrolyte for solid state batteries

Employing low Tg polymers has fundamental limitations in providing the desirable ionic conductivity at ambient temperature due to the freezing of chain dynamics. The stiffening of polymer chains and the formation of highly ordered systems due to the crosslinks have influenced the ionic conductivity. Ionic conductivity of 1.02 × 10-5 S cm-1 was attained for the system that presented a quantum mechanical tunnelling mode of ion transport. A Na-ion transference number of 0.31 was achieved for 30 wt% of NaClO4 salt in a polycaprolactone (PCL) matrix with an electrochemical stability window of 3.6 V at 25 °C. High crystallinity and limited availability of free Na+ ions in the electrolyte have resulted in lower ionic conductivity. PCL-NaClO4 exhibited brilliant thermal stability and mechanical properties. The influence of cathode materials MnO2, V2O5 and I2 on the discharge characteristics of an electrochemical cell in the configuration cathode |(70 wt%)PCL-NaClO4(30 wt%)|Na has been studied.