Two types of ion-conducting polyimides with sulfonate or ether functional groups were synthesized as ion-type or coordination-type cathode binders for lithium-ion batteries (LIBs), respectively. Although superior ion transport abilities have been reported for both types of ion-conducting polymers, their electrochemical performances are significantly different and the corresponding transport mechanisms at the electrolyte/electrode interface remain elusive. Here, we combine experimental and computational techniques to investigate the cathode interface in the presence of both functional polymer binders in comparison with the poly(vinylidene fluoride) (PVDF) binder as reference. A broad shoulder in the cyclic voltammogram accompanied by a poor rate performance of battery tests was observed for a LiFePO4 cathode with coordination-type ether-based polyimide (EPI) binder. In contrast, a LiFePO4 cathode with ion-type sulfonated polyimide (SPI) binder exhibits smaller concentration polarization, achieving satisfactory capacity at high current density. Simulations show that the ether-based binder strongly coordinates Li ions and thus slows the diffusion of Li ions. This leads to the reduction of the LIB electrochemical performance at a high C-rate. In contrast, the negative moiety of the SPI binder leads to less localization of Li ions, allowing a slightly higher Li-ion mobility. Conventional PVDF shows no affinity to Li ions, leading to less Li-ion accumulation at the electrode/electrolyte interface. Yet, the cathode surface covered with PVDF shows the lowest Li-ion diffusivity compared to those with the two types of Li-ion-conducting binders. Therefore, cathodes with SPI and PVDF binders show less polarization at the electrode interface and allow higher C-rate performance of LIBs. The combined results provide a comprehensive understanding of the mechanism of ion conduction in ion- and coordination-type Li-ion-conducting polymer binders. This gives valuable insight into the design of next-generation polymer materials for high-power LIBs.
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