Polymer chemistry can now provide remarkable control over polymer microstructures, including the placement of associating functional groups in ionomers. We have studied various precise and nearly-precise polymer architectures focusing on connecting the self-assembled morphologies and transport properties. This talk will highlight a set of segmented ionomers containing polar units with one neutralized sulfonate groups separated by a precise number (n = 10 - 48) of methylene groups (PESn-X). These PESn-X ionomers exhibit exceptional long-range order and order-order transitions reminiscent of block copolymers and we have constructed phase diagrams for comparison with theoretical predictions of multiblock copolymers. The PES12-Li polymer exhibits a disordered morphology above 120C and we applied the RPA theory for multiblock copolymers to extract the chi parameter. With respect to ion conductivity, the most promising of the ordered structures is the double gyroid structure that exhibits higher ionic conductivity than the isotropic layered or hexagonal morphologies. Finally, we are exploring additives to further increase the ionic conductivity in these and other precise ionomers.

Nanostructured ionomers for ion transport

ACS Fall 2021

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