Differential voltage analysis as a tool for analyzing inhomogeneous aging: A case study for LiFePO4|Graphite cylindrical cells

In this work the differential voltage analysis (DVA) is evaluated for LiFePO4|Graphite cylindrical cells aged in calendaric and cyclic tests. The homogeneity of the active lithium distribution and the loss of anode active material (LAAM) are measured by the characteristic shape and peaks of the DVA. The results from this analysis exhibit an increasing homogeneity of the lithium-ion distribution during aging for all cells subjected to calendaric aging. At 60 °C, LAAM is found additionally and can be associated with the deposition of dissolved Fe from the cathode on the anode, where it finally leads to the clogging of pores. For cells aged under cyclic conditions, several phenomena are correlated to degradation, such as loss of active lithium and local LAAM for 100% DOD. Moreover, the deactivation of certain parts of anode and cathode due to a lithium-impermeable covering layer on top of the anode is observed for some cells. While the 100% DOD cycling is featured by a continuous LAAM, the LAAM due to deactivation by a covering layer of both electrodes starts suddenly. The homogeneity of the active lithium distribution within the cycled cells is successively reduced with deposited passivation layers and with LAAM that is lost locally at positions with lower external pressure on the electrode.