Mixed Ionic–Electronic Conduction Increases the Rate Capability of Polynaphthalenediimide for Energy Storage

Conjugated polymers offer a number of unique and useful properties for use as battery electrodes, and recent work has reported that conjugated polymers can exhibit excellent rate performance due to electron transport along the polymer backbone. However, the rate performance depends on both ion and electron conduction, and strategies for increasing the intrinsic ionic conductivities of conjugated polymer electrodes are lacking. Here, we investigate a series of conjugated polynapthalene dicarboximide (PNDI) polymers containing oligo(ethylene glycol) (EG) side chains that enhance ion transport. We produced PNDI polymers with varying contents of alkylated and glycolated side chains and investigated the impact on rate performance, specific capacity, cycling stability, and electrochemical properties through a series of charge–discharge, electrochemical impedance spectroscopy, and cyclic voltammetry measurements. We find that the incorporation of glycolated side chains results in electrode materials with exceptional rate performance (up to 500C, 14.4 s per cycle) in thick (up to 20 μm), high-polymer-content (up to 80 wt %) electrodes. Incorporation of EG side chains enhances both ionic and electronic conductivities, and we found that PNDI polymers with at least 90% of NDI units containing EG side chains functioned as carbon-free polymer electrodes. This work demonstrates that polymers with mixed ionic and electronic conduction are excellent candidates for battery electrodes with good cycling stability and capable of ultra-fast rate performance.