The mechanisms driving the thermo-electrochemical response of commercial lithium-ion cells under extreme overdischarge conditions (< 0.0 V) are investigated in the context of copper dissolution from the anodic current collector. A constant current discharge with no lower cutoff voltage was used to emulate the effects of forced overdischarge, as commonly experienced by serially connected cells in an unbalanced module. Cells were overdischarged to 200% DOD (depth of discharge) at C/10 and 1C rates to develop an understanding of the overdischarge extremes. Copper dissolution began when a cell reached its minimum voltage level (between −1.3 V and −1.5 V), where the anode potential reached a maximum value of ∼4.8 V vs. Li/Li + . Deposition of copper on the cathode, anode, and separator surfaces was observed in all overdischarged cells, verified with EDS/SEM results, which further suggests the formation of internal shorts, although the cell failures proved to be relatively benign. The maximum cell surface temperature during overdischarge was found to be highly rate-dependent, with the 1C-rate cell experiencing temperatures as high as 79 • C. Concentration polarization and solid electrolyte interphase (SEI) layer breakdown prior to the initiation of copper dissolution are proposed to be the main sources of heat generation during overdischarge.

The metastability of lithium electrodeposition continues to be a scientific mystery. Local ionic depletion has been conventionally argued to be a root cause for nonlinear morphological manifestations. Given the bulk nature of electrolyte transport limitation, it should be absent for very small interelectrode separations; however, even under such conditions, sustained electrodeposition is not observed. We find that the passivating film formed due to lithium's high reactivity alters the surface energies and in turn deposition preference for fresh lithium. This asymmetry in deposition preference leads to nonuniform surface structure growth and traps the electrolyte layer. Such electrolyte confinement causes polarization, even at subcritical currents. The existence of confined electrolyte and associated electrochemical complexations is proved through temperature-controlled electrodeposition experiments.Letter http://pubs.acs.org/journal/aelccp

Overdischarge is a potential problem in large battery packs since cells in a series string are discharged under the same load, despite having different capacities. Although a single overdischarge does not necessarily cause a safety hazard, it forces electrodes outside their safe potential range and adversely affects the integrity of cell components. This work aims to fill the knowledge gap about the combined effect of aging-induced and overdischarge–induced degradation mechanisms. Graphite/LCO pouch cells are cycled at a moderate rate using four lower cutoff voltages: 2.7 V, 1.5 V, 0.0 V, and −0.5 V. The cells aged above the onset of reverse potential have an extended cycle life with aging-induced solid electrolyte interphase (SEI) growth and electrolyte decomposition as the main degradation mechanisms. In contrast, the cells aged under reversal condition (Elower ≤ 0.0 V) exhibit fast degradation, dictated by the interplay among lithium plating, cathode particle cracking, and dissolution of Cu current collector. The analysis is complemented with a comparative study of various state of health (SoH) indicators, including an internal resistance based dimensionless SoH descriptor. The results prove that overdischarge-induced abuse although benign, may turn into a malignant condition when alternated with continuous charging.

Existing in operando methods for detection of plated lithium can only detect the presence of plating after the charge is complete and irreversible damage has already occurred. In this work, the characteristic potential minimum on the graphite electrode during high rate lithiation is proposed and assessed as an in operando technique for detecting the onset of lithium plating. While other studies have shown that rapid self-heating of a cell can cause this type of "voltage overshoot", we confirm through temperature-controlled coin cell experiments that such a voltage profile can also be caused by the occurrence of severe lithium plating. In cells which demonstrated voltage overshoot, macroscopically observable lithium plating films were present on the graphite electrodes upon disassembly, resulting in very poor single-cycle Coulombic efficiency. The significance of this voltage characteristic is confirmed through direct observation of the onset of lithium plating in an in situ optical microscopy cell. We observe that the growth of large metallic lithium deposits within the porous electrode structure can cause swelling and cracking of the graphite electrode, suggesting loss of active material due to mechanical electrode degradation as an important consequence of severe lithium plating.

Overcharge presents a serious safety concern for large scale applications of Li-ion batteries. Despite the availability of several studies of aging-induced and overcharge-induced degradation, there still exists a knowledge gap of what would happen if both degradation mechanisms simultaneously occur. In this work, commercial graphite/LCO pouch cells (5 Ah) are continuously cycled at different upper cutoff voltages, 4.2 through 4.8 V, to elucidate the cumulative effect of the overcharge process on the long-term cycling. As the upper cutoff voltage is extended, the cell gains a higher initial capacity but the cycle life diminishes significantly. Cells overcharged beyond 4.5 V experience significant volume expansion and a high rate of capacity fade, as well as a considerable increase in the temperature and internal resistance. Lithium plating and electrolyte decomposition are observed in cells charged beyond 4.5 V, with SEM-EDS verifying their presence. Electrochemical evidence of both degradation modes appears as a voltage undershoot in the discharge curves. A comparative study of various State of Health (SoH) estimation parameters is presented with the introduction of a new dimensionless SoH indicator, ΦR, based on internal resistance measurement. The proposed degradation number is found to be a good indicator of aggravated degradation in Li-ion cells.