Influence of Backbone on the Performance of Pendant Polymer Electrode Materials in Li-ion Batteries

Pendant polymers are a promising class of electrode materials due to their synthetic simplicity, derivation from sustainable feedstocks, and potentially benign synthesis. These materials consist of a redox-active pendant tethered to a polymer backbone, which mitigates dissolution during electrode cycling. To date, an extensive number of pendant groups have been studied within the context of metal-ion batteries. However, the choice of the polymer backbone and its impact on the electrode performance have been relatively understudied. In this work, we use a postpolymerization modification approach to synthesize a series of viologen-bearing redox-active pendant polymers with similar molecular weights but three distinct chemical backbones, namely, polyacrylamide, polymethacrylamide, and polystyryl. By evaluating the polymers in lithium-ion batteries, we show that the polymer backbone has a significant influence on electrode performance and behavior. Specifically, the polymethacrylamide displays slower kinetics than the other two polymers, resulting in lower capacities, particularly at high cycling rates. Furthermore, the charge storage mechanism is dependent on the nature of the backbone: the polyacrylamide shows a significant capacitive contribution to charge storage, while the polystyryl does not. The difference in performance between the polymer electrode materials is ascribed to a difference in chain mobility and packing within the electrode films. Overall, this work shows that the fundamental properties of the polymer backbone are critical to the design of high-performance polymer electrodes.