Cross-linked block copolymer/ionic liquid self-assembled blends for polymer gel electrolytes with high ionic conductivity and mechanical strength

摘要

Poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO) block copolymers (BCPs) with cross-linkable end groups were synthesized, blended with an ionic liquid (IL) diluent, and cross-linked to form polymer gel electrolytes. The IL prevented crystallization of PEO at high concentrations, enabling fast ion transport. In addition, the IL was selective for the PEO block, inducing strong microphase separation in what are otherwise disordered or weakly ordered BCP melts. Cross-linking the BCPs in the presence of the IL resulted in the formation of solid, elastic gels with high ionic conductivities - greater than 1.0 mS/cm at 25 C for some compositions. However, it was found that neither the presence or absence of microphase separation nor the BCP composition of the microphase separated gels substantially influenced ionic conductivity. Increasing the cross-link density through the use of phase-selective PEO- and PPO-based cross-linking reagents was also evaluated. It was revealed that confinement of cross-links to the PPO rich domains through the use of PPO-based diacrylates enhanced the mechanical strength of the gels without detriment to the ionic conductivity. Conversely, cross-linking in the PEO-rich domains through the use of PEO-based acrylates significantly reduced conductivity. Isolation of cross-links within a minor nonconducting domain in a microphase separated gel is a viable strategy for mechanical property enhancement without a large sacrifice in conductivity, effectively decoupling ionic conductivity and mechanical strength. This approach yielded solid-like gel electrolytes fabricated from BCPs that can be produced inexpensively, with ionic conductivities of 0.64 mS/cm at 25 C and a frequency independent storage modulus of approximately 400 kPa.