Carbonyl-Containing Solid Polymer Electrolyte Host Materials: Conduction and Coordination in Polyketone, Polyester, and Polycarbonate Systems

Research on solid polymer electrolytes (SPEs) is now moving beyond the realm of polyethers that have dominated the field for several decades. A promising alternative group of candidates for SPE host materials is carbonyl-containing polymers. In this work, SPE properties of three different types of carbonyl-coordinating polymers are compared: polycarbonates, polyesters, and polyketones. The investigated polymers were chosen to be as structurally similar as possible, with only the functional group being different, thereby giving direct insights into the role of the noncoordinating main-chain oxygens. As revealed by experimental measurements as well as molecular dynamics simulations, the polyketone possesses the lowest glass transition temperature, but the ion transport is limited by a high degree of crystallinity. The polycarbonate, on the other hand, displays a relatively low coordination strength but is instead limited by its low molecular flexibility. The polyester performs generally as an intermediate between the other two, which is reasonable when considering its structural relation to the alternatives. This work demonstrates that local changes in the coordinating environment of carbonyl-containing polymers can have a large effect on the overall ion conduction, thereby also showing that desired transport properties can be achieved by fine-tuning the polymer chemistry of carbonyl-containing systems.This work has been financed through support from ECO2LIB (European Union H2020 research and innovation programme under grant agreement no. 875514), ERC (grant no. 771777 FUN POLYSTORE), the Swedish Foundation for Strategic Research (project SOLID ALIBI, grant no. 139501338), the Swedish Foundation for International Cooperation in Research and Higher Education (STINT) together with the Swedish Research Council (VR) (project MG2019-8467 WInter+SPE), and STandUP for Energy. The simulations were performed on the resources provided by the Swedish National Infrastructure for Computing (SNIC) at PDC. We sincerely thank Prof. Dr. T. Isono and Prof. Dr. T. Satoh (Hokkaido University) for the suggestions on the GPC analysis