Measurements of lithium-ion concentration equilibration processes inside graphite electrodes

Methods for estimating inner states in a lithium-ion cell require steady state conditions or accurate models of the dynamic processes. Besides often used inner states such as state-of-charge, state-of-health or state-of-function, relaxation processes strongly influence the mentioned states. Inhomogeneous utilization of electrodes and consequent limitations in the operating conditions have recently been brought to attention. Relaxation measurements after an inhomogeneous current distribution through the thickness of an electrode have not been addressed so far. By using a previously developed laboratory cell, we are able to show an inhomogeneous retrieval of lithium-ions from a graphite electrode through the layer with spatial resolution. After this inhomogeneity caused by a constant current operation, equilibration processes are recorded and can be assigned to two different effects. One effect is an equilibration inside the particles (intra-particle) from surface to bulk and vice versa. The other effect is an assimilation between the particles (inter-particle) to reach a homogeneous state-of-charge in each particle throughout the electrode layer. While intra-particle relaxation is observed to be finished within 4 h, inter-particle relaxation through the layer takes more than 40 h. The overall time for both equilibration processes shows to be in the order of 48 h.