The behavior of a many particle cathode in a lithium-ion battery

Abstract

We study the almost reversible storage process of charging and discharging of lithium-ion batteries. That process is accompanied by a phase transition and charging and discharging run along different paths, so that hysteretic behavior is observed. We are interested in the storage problem of the cathode of a lithium-ion battery consisting of a system of many iron phosphate (FePO4) particles. There are mathematical models, see [DGJ08], [DGGHJ09] and [DG09], that describe phase transitions and hysteresis exclusively in a single storage particle and they can describe the observed hysteretic voltage-charge plots with almost horizontal plateaus. Interestingly the models predict that the coexistence of a 2-phase system in an individual particle disappears, if its size is below a critical value. The disappearance of the phase transition in the single particle model implies the disappearance of the hysteresis. However, in the experiment hysteretic behavior survives. In other words: The behavior of a storage system consisting of many particles is qualitatively independent of the fact whether the individual particles itself develop a 2-phase system or if they remain in a single phase state. This apparent paradoxical observation will be resolved in this article by a many particle model. It will be shown that if each of the individual particles is in a homogeneous state, nevertheless the many particle ensemble exhibits phase transition and hysteresis ...