Design of superionic polymers—New insights from Walden plot analysis

Using a modified Walden plot analysis, we demonstrate that polyether-based solid electrolytes have intrinsic limitations for ionic transport at ambient and low temperatures, due to strongly coupled segmental and ion dynamics. On the other hand, rigid polymers can exhibit ionic conductivity that is highly decoupled from segmental relaxation, thus providing a significant advantage over traditional polyether electrolytes. Our analysis emphasizes that decoupling of ionic transport from segmental dynamics is the key for macromolecular design of “superionic” polymers.