Understanding evolution of lithium trivanadate cathodes during cycling via reformulated physics-based models and experiments

Degradation of lithium trivanadate (Li_xV₃O₈) cathodes has been widely reported in the literature, but studies have offered little insight towards developing a detailed understanding of the evolution of the active material, and have been inconclusive as to the root cause of degradation. Here, we refit a validated physics-based model to discharge curves over the course of cycling at C/5, and use the evolution of the model parameters to track evolution of the cathode. A regularization penalty for adjusting model parameters from the validated model is introduced as a framework to identify which model parameters can explain a significant portion of the observed change in the voltage profile over the course of cycling. SEM reveals that lithium trivandate particles fracture upon cycling at C/5, consistent with the results of the parameter estimation, deactivation of lithium trivanadate and faster diffusion of lithium within the active particles. The physics-based model is then used to design modified cycling protocols which identify the phase transformation during discharge of lithium trivanadate as the driver of the particle fracture and capacity fade.