OCV Hysteresis in Li‐Ion Batteries including Two‐Phase Transition Materials

The relation between batteries′ state of charge (SOC) and open‐circuit voltage (OCV) is a specific feature of electrochemical energy storage devices. Especially NiMH batteries are well known to exhibit OCV hysteresis, and also several kinds of lithium‐ion batteries show OCV hysteresis, which can be critical for reliable state estimation issues. Electrode potential hysteresis is known to result from thermodynamical entropic effects, mechanical stress, and microscopic distortions within the active electrode materials which perform a two‐phase transition during lithium insertion/extraction. Hence, some Li‐ion cells including two‐phase transition active materials show pronounced hysteresis referring to their open‐circuit voltage. This work points out how macroscopic effects, that is, diffusion limitations, superimpose the latte‐ mentioned microscopic mechanisms and lead to a shrinkage of OCV hysteresis, if cells are loaded with high current rates. To validate the mentioned interaction, Li‐ion cells′ state of charge is adjusted to 50% with various current rates, beginning from the fully charged and the discharged state, respectively. As a pronounced difference remains between the OCV after charge and discharge adjustment, obviously the hysteresis vanishes as the target SOC is adjusted with very high current rate.