Relaxation-Induced Memory Effect of LiFePO₄ Electrodes in Li-Ion Batteries

In Li-ion batteries, memory effect has been found in several commercial two-phase materials as a voltage bump and a step in the (dis)charging plateau, which delays the two-phase transition and influences the estimation of the state of charge. Although memory effect has been first discovered in olivine LiFePO₄, the origination and dependence are still not clear and are critical for regulating the memory effect of LiFePO₄. Herein, LiFePO₄ has been synthesized by a home-built spray drying instrument, of which the memory effect has been investigated in Li-ion batteries. For as-synthesized LiFePO₄, the memory effect is significantly dependent on the relaxation time after phase transition. Besides, the voltage bump of memory effect is actually a delayed voltage overshooting that is overlaid at the edge of stepped (dis)charging plateau. Furthermore, we studied the kinetics of LiFePO₄ electrode with electrochemical impedance spectroscopy (EIS), which shows that the memory effect is related to the electrochemical kinetics. Thereby, the underlying mechanism has been revealed in memory effect, which would guide us to optimize two-phase electrode materials and improve Li-ion battery management systems.