Spatiotemporal Analysis of Graphite Electrode Aging Through X-rays

Abstract: Aging limits commercial lithium-ion battery lifetime and must be understood at the level of active materials to improve both cell durability and performance. We show that in state-of-the-art technologies such as graphite/LiFePO4-Li(NiCoAl)O2 cells, degradation mostly arises at the negative electrode side due to both loss of active material and cyclable lithium. The characteristics of these phenomena are unraveled by applying a multi-technique workflow in which electrochemical, structural, and morphological analyses are combined. Series of post mortem, ex situ and operando experiments performed on aged materials dismounted from a large format cell at its end-of-life are benchmarked against pristine materials to highlight how in-plane and through-plane heterogeneities in graphite dynamics are profoundly modified in nature and exacerbated by aging. We discover inactive regions, where pure graphite or lithiated phases (LixC6) are invariant on cycling. They correspond to particles either disconnected (irreversibly lost) or kinetically-limited (reactivated at a very slow C-rate). As we map their distribution in 2D during battery cycling, we observe that LixC6-inactivity is heterogeneously distributed in the depth of the aged negative electrode and depends on both the x value and the C-rate. In particular, the negative electrode-separator interface is much more inactivated after long-term usage. Inactivity is correlated with an overall increased spatial heterogeneity of lithium concentration. This work suggests that the origin of aging lies in overworking graphite close to the separator.