Electrochemical characterisation of degradation mechanisms in lithium- and sodium-ion batteries during overdischarge
- Lithium-iron-phosphate (LFP) and sodium-ion batteries (SIBs) are promising technologies for energy storage systems due to their safe handling and cost-effectiveness. SIBs can be discharged to 0V without the safety concerns associated with lithium-ion batteries' copper current collector oxidation. However, overdischarging both types of batteries may decompose and subsequently rebuild the solid electrolyte interphase (SEI), leading to irreversible capacity loss and degradation.
This study performs an in-situ analysis of the overdischarge process of LiFePO4 pouch and Na-ion cylindrical cells. Therefore, the cells are characterised for three low C-rate constant current or three slow-scan voltage cycles. While the voltage range of the manufacturer’s specifications is chosen for the first and third cycle, for the second cycle the minimum voltage is modified to 0.5V (LFP) and 0V (SIB), respectively. This enables tracing the degradation during the overdischarge, as well as through aLithium-iron-phosphate (LFP) and sodium-ion batteries (SIBs) are promising technologies for energy storage systems due to their safe handling and cost-effectiveness. SIBs can be discharged to 0V without the safety concerns associated with lithium-ion batteries' copper current collector oxidation. However, overdischarging both types of batteries may decompose and subsequently rebuild the solid electrolyte interphase (SEI), leading to irreversible capacity loss and degradation.
This study performs an in-situ analysis of the overdischarge process of LiFePO4 pouch and Na-ion cylindrical cells. Therefore, the cells are characterised for three low C-rate constant current or three slow-scan voltage cycles. While the voltage range of the manufacturer’s specifications is chosen for the first and third cycle, for the second cycle the minimum voltage is modified to 0.5V (LFP) and 0V (SIB), respectively. This enables tracing the degradation during the overdischarge, as well as through a comparison of the results pre- and post-overdischarging. For this purpose, the study employs two electrochemical characterisation techniques: differential voltage analysis (DVA) and cyclic voltammetry (CV). While cyclic voltammetry allows for the study of the kinetics of electron transfers [1], DVA enables the assessment of lithium distribution homogeneity and capacity degradation [2].
In both cells, the characterisation shows significant differences before and after overdischarging, indicating lasting changes through the decomposition and rebuilding of the SEI. This comparative study elucidates the overdischarge-induced degradation in sodium- and lithium-ion batteries, highlighting the utility of CV and DVA in analysing degradation mechanisms.…

