Reversible Capacity Losses in LiFePO4 / Graphite Cells

Abstract

This investigation focuses on significant capacity losses that have been found to occur in commercial lithium-iron phosphate (LFP) / graphite cells after repeated shallow cycling around medium states of charge (SOCs). Many combinations of cycle depth, medium SOC and temperature are examined over up to 10,000 full cycle equivalents. Up to 1000 full cycle equivalents, the capacity loss rate is four times higher when the cells are cycled between 40% and 60% state of charge than it is with full cycles. It is shown that these extraordinary losses occur in three different lithium-iron phosphate / graphite cell models, two 26650-type and one 18650-type, but do not occur in a nickel-manganese-oxide / graphite 18650-type cell. Most of the apparently lost capacity is shown to be recoverable by holding the cells at either 0 % or 100 % state of charge over a period of several days. Differential voltage analysis and visual post-mortem inspection as well as coin cell experiments with harvested electrode material suggest that these capacity losses are caused by strongly non-uniform lithium distributions in the electrodes. Hypothetical mechanisms are presented and discussed that could lead to such non-uniform distributions of lithium forming preferentially in lithium-iron phosphate based cells. The findings presented in this study are believed to be particularly relevant for grid applications like primary control reserve or in other scenarios where the battery mainly serves as a peak power buffer, e. g. in hybrid drivetrains.The graph shows the capacity evolution of LFP / graphite cells cycled with full cycles and with 20 % cycle depth around three different medium SOCs. Capacity loss is largest when cycling between 40 % and 60 % SOC. The photographs show post-mortem views of the graphite anodes of three different LFP / graphite cell models that were cycled using this procedure until reaching ca. 80 % remaining capacity. Gold colored stripes at the top and the bottom of the electrodes indicate a non-uniform distribution of intercalated lithium. Figure 1