考虑应力耦合的电化学反应模型：修正Butler-Volmer模型及其应用

he present paper investigates the impacts of stress coupling on electrochemical reaction of intercalation/deintercalation in a lithium ion battery. Based on the traditional Butler-Volmer model which describes the kinetics of electrode reaction and ignores stress coupling, elastic energy, which arises from the deformation and stress of an electrode, was firstly introduced into the free energy system. After that, the impacts of variation of free energy under electro-mechanical coupling condition on the forward and reverse reaction were comprehensively evaluated. Finally, the Electrochemical reaction rate and current density were obtained and further employed to establish the modified electrochemical model with consideration of stress coupling. It is found that compressive stress raises the energy barrier in the direction of lithiation by improving the free energy, and therefore hinder the intercalation of lithium ions from electrolyte into active material. At last, according to the modified Butler-Volmer model, the lithiation procession of a Si thin film electrode was simulated and further compared with experiments.