The Complex and Spatially Heterogeneous Nature of Degradation in Heavily Cycled Li-ion Cells

Abstract As service lifetimes of electric vehicle (EV) and grid storage batteries continually improve, it has become increasingly important to understand how cells perform after extensive cycling. The multifaceted nature of degradation in Li-ion cells can lead to complex behavior that may be difficult for battery management systems or operators to model. Accurate characterization of heavily cycled cells is critical for developing accurate models, especially for cycle-intensive applications like second-life grid storage or vehicle-to-grid charging. In this study, we use operando synchrotron X-ray diffraction (SR-XRD) to characterize a commercially manufactured polycrystalline NMC622 pouch cell that was cycled for more than 2.5 years. Using spatially resolved synchrotron XRD, the complex kinetics and spatially heterogeneous behavior of such cells can be mapped and characterized under both near-equilibrium and non-equilibrium conditions. The resulting data is complex and multifaceted, requiring a different approach to analysis and modelling than what has been used in the literature. To show how material selection can impact the extent of degradation, we compare the results from polycrystalline NMC622 cells to an extensively cycled single-crystal NMC532 cell with over 20,000 cycles – equivalent to a total EV traveled distance of approximately 8 million km (5.5 million miles) over six years.