Gas generation within Li-ion batteries (LIB) can lead to an increase in resistance, thereby, reducing their cycle lifetime. The chance of catastrophic failure via internal gas evolution may increase as a function of cell size and capacity. However, in-situ studies of gas evolution at the cell level are very limited due to limited number of techniques that can effectively probe this. Hence, for the first time, we employed high-energy X-ray tomography to non-destructively observe the structural evolution (gas and electrodes) as a function of cycle numbers for a 400 mAh commercial Li-ion pouch cell. Gas agglomeration led to cell deformation in different areas were observed in 4D (3D + time), the subsequent quantification including the volume fraction, surface area and thickness showed a heterogeneous gas distribution, revealing the degradation mechanism involving the coalescence of gas. This study demonstrates a feasible case of the use of lab-based X-ray to investigate the cell degradation and monitor state of health (SOH) by tracking the thickness in-situ, providing practical guidance for designing safer pouch cells
