Charging dependent electro-chemo-mechanical coupling behavior of polymer electrolytes containing immobilized anions

Theoretical models have been developed to explore the electrodeposition stability between Li metal and salt-doped polymer electrolytes. However, there is still limited investigation on the coupling behavior between mechanics and electrochemistry in those novel nano-structured polymers with immobilized anions. In this work, we employ a multiphysics modeling framework to predict the electro-chemo-mechanical behavior of polymer electrolytes containing immobilized anions. We analyze the impacts of charging conditions, stress coupling and the immobilization of anions on their ion transport, electrical and mechanical properties during charging. Strengthening stress coupling is demonstrated to improve the diffusion-driven stability of electrodeposition, by enhancing limiting applied current densities. Compared with stress coupling, immobilizing anions surprisingly sustains the non-zero interfacial Li⁺-ion concentrations even at high applied currents, thereby mitigating the potential diffusion-driven instability of electrodeposition. Both stress/strain and overpotentials also get reduces with increasing the concentrations of immobilized anions. This theoretical work provides insights into the strategy of redesigning polymer electrolytes, and also lays foundation for the multiphysics modeling of electrodes and full-cell battery systems.