Effects of cycling on lithium-ion battery hysteresis and overvoltage

Currently, lithium-ion batteries are widely used as energy storage systems for mobile applications. However, a better understanding of their nature is still required to improve battery management systems (BMS). Overvoltages and open-circuit voltage (OCV) hysteresis provide valuable information regarding battery performance, but estimations of these parameters are generally inaccurate, leading to errors in BMS. Studies on hysteresis are commonly avoided because the hysteresis depends on the state of charge and degradation level and requires time-consuming measurements. We have investigated hysteresis and overvoltages in Li(NiMnCo)O₂/graphite and LiFePO₄/graphite commercial cells. Here we report a direct relationship between an increase in OCV hysteresis and an increase in charge overvoltage when the cells are degraded by cycling. We find that the hysteresis is related to diffusion and increases with the formation of pure phases, being primarily related to the graphite electrode. These findings indicate that the graphite electrode is a determining factor for cell efficiency.