Stepwise Structural Relaxation in Battery Active Materials

Whenever the cycling of Li-ion batteries is stopped, the electrode materials undergo a relaxation process, but the structural changes that occur during relaxation are not well-understood. We have used operando synchrotron X-ray diffraction with a time resolution of 1.24 s to observe the structural changes that occur when the lithiation of graphite and LiFePO₄ electrodes are interrupted. Assessing the kinetics of the relaxation processes coupled with molecular dynamics simulations allows us to identify three relaxation stages in graphite. The atomistic origin for the relaxation process within the partially lithiated graphite structure is driven by the reorganization of Li ions into Li clusters. Relaxation in LiFePO₄ electrodes is considerably slower than for graphite, but the observed structural changes is also attributed to reorganization of Li ions. These insights highlight the nature of the structural changes that occur during relaxation and the importance of using operando structural studies to avoid misleading conclusions about the reaction mechanisms in battery materials.