Organic radical polymers are promising electrode material candidates for organic batteries, with the potential to improve sourcing, safety, flexibility, and recyclability, relative to current lithium-ion battery technologies. These materials, which contain redox-active pendant groups tethered to a (non-conjugated) polymer backbone, offer exquisite synthetic and functional flexibility due to their modular structure. However, accurate prediction of their functional properties, particularly the charge-transport properties at the polymer-polymer interface, requires simulation of structure and dynamics over long length and time scales.<br/> <br/>Here, we present our efforts on the multiscale simulation of redox-active radical polymers at multiple states of charge. We consider both model systems (viologen- and TEMPO-based polymers) and polymers with redox-active groups identified as promising next-generation candidates based on their molecular level electrochemical properties. Our model combines atomistic molecular simulation and quantum chemistry to quantify the impact of molecular and polymer properties (e.g., reorganization energy, polymer repeat-unit diffusion, counter-ion diffusion) on the charge transfer kinetics. Both inter- and intrapolymer charge transfer are considered. We compare our results to experimental measurements of conductivity when possible and provide a sensitivity analysis of our model for cases where experiments are not yet available.

Identification of the key molecular and polymeric levers for maximizing the conductivity of non-conjugated radical polymers via molecular simulation

ACS Spring 2022

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