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IMPLICATIONS OF OFF-NOMINAL CONDITIONS ON LI-ION BATTERY DEGRADATION AND CYCLE LIFE
Recently, energy storage systems have become more focused towards sustainable energy sources like LIBs due to attractive attributes like high energy density and volumetric density which make them extremely competitive compared to other energy sources for many portable and non-portable applications (smartphones, eVTOLs, stationary storage systems, electric vehicle and so on). Longer cycling stability, capacitance retentive power, lower self-discharge rate and high voltage window are qualitative features in LIB. Even though LIBs are rechargeable energy storage systems, all cells decay and degrade over time causing capacity and power fade due to a number of factors such as manufacturing defects, usage outside the normal operating conditions, and other abuse conditions like overcharge, over-discharge and indentation. This work presents a systematic investigation of several off-nominal conditions which are typically observed in LIBs such as overcharge, over-discharge, nail indentation, periodic overcharge, and over-discharge in order to form a comparative analysis on the effect of each of these conditions on cycle life aging, morphological changes on the cell components and also to evaluate potential internal short circuit (ISC) mechanisms. The cell failure mechanism induced by each condition and its negative impact on the electrochemical performance has been rigorously analyzed in this work based on the proper protocols. The correlation of the galvanostatic performance with the morphological change of the individual electrodes was also scrutinized under SEM and EDS to demarcate the severity of the defect into Li-ion cells. The practical off-nominal condition analysis of LIB will pave the way for more reliable cell functioning and recommendations to be considered to effectively analyze these off-nominal conditions. The analysis was divided into two parts; 1) curve-based analysis which included capacity fade, internal resistance, Incremental & Differential capacity analysis and EIS analysis 2) disassembly-based analysis which consisted of post-mortem visual inspection, morphology-based analysis using electron microscopy and composition analysis. From the capacity fade and IR evolution study, it was observed that periodic off-nominal conditions exhibited the highest rate of capacity fade and the greatest increase in DC internal resistance consistently. The least rate of capacity loss was shown by overcharged and no defect cells and a similar trend for DCIR values as well indicating that there was a positive correlation between capacity fade and internal resistance evolution. From the EIS study a slightly different trend was observed with the overcharged cell exhibiting the highest ohmic resistance and the no defect cell XV
the least indicating ORI as an aging mechanism in overcharged and periodic overcharge/over-discharged cells. Another interesting observation was that the highest change in change transfer resistance was shown by over-discharged cell followed by nail-indented and overcharged cells and the least for cells subjected to periodic off-nominal conditions. This was attributed to a large amount of delamination caused by particle cracking in no defect cells causing LAM in these cells, lithium plating in Overcharged, copper current collector dissolution in over-discharged cells which resulted in LLI as the primary aging mechanism in these cells. This was further confirmed by ICA-DVA curve analysis at various capacity fades, postmortem inspection and SEM-EDS analysis. The periodic overcharged cells underwent a combination of degradation mechanisms including LAM from delamination, LLI through lithium deposition on the separators and Contact loss due to electrolyte vaporization causing active material adhesion on the separator and vice versa. The last degradation mechanism exacerbated the rate of increase of internal resistance by blocking pathways for Li+ ion diffusion. To summarize, while no defect and nail-indented cells exhibited primarily one aging mechanism (ORI) other cells exhibited a combination of degradation modes and the decoupling of these modes became increasingly indistinguishable for the cells subjected to periodic off-nominal conditions. Interestingly, no manifestation of soft or hard Internal short circuits was observed in the tested cells. However, it should be noted that for the periodic overcharged cells which underwent excessive lithium plating on the separators and charring of electrodes, dendrite formation could potentially have caused ISC upon further cycling. This cements the fact that periodic off-nominal conditions exacerbate the possibility of sudden failures and accelerate degradation in Li-ion cells.
- Master of Science
- Mechanical Engineering
- West Lafayette