Yingzhi Cui

Lithium deposition on graphite anode during long-term cycles and the effect on capacity loss

Lithium deposition on the surface of a graphite anode during long-term cycles was evaluated using a LiCoO2/graphite battery. The batteries were charged/discharged at 1 C and 25 °C within the voltage range of 2.75–4.2 V for 600, 700, 800, 900 and 1000 cycles. Scanning electron microscopy (SEM) results indicated that both solid electrolyte interphase (SEI) film and lithium deposition appeared on the surface of the cycled graphite anode. Dendritic and granular lithium deposits grew on the anode non-uniformly. Metallic lithium existed in the deposition according to differential scanning calorimetry (DSC) results. Capacity declined distinctly from the 800th cycle, corresponding with the growth of lithium deposits. An SEI film was formed on the surface of the lithium deposits. Results of X-ray photoelectron spectroscopy (XPS) test indicated that the composition of SEI film on the surface of the lithium deposits was the same as that of the SEI film on the surface of cycled graphite. Capacity loss from the electrolyte consumed by the formation of the SEI film was 23.61%, while the loss from other battery components was 76.39%. Formation of lithium deposits consumed active lithium in the battery and led to capacity loss. According to test results of the three-electrode cell, the average anode potential at the end of constant-current charging for full battery became more negative with the cycling, and this phenomenon was related to the generation of lithium deposits.

Lithium compound deposition on mesocarbon microbead anode of lithium ion batteries after long-term cycling.

Lithium compound deposition on mesocarbon microbead (MCMB) anode after long-term cycling was studied in LiCoO2/MCMB battery. Lithium compound deposition did not generate on the activated MCMB anode, but it generated unevenly on the long-term cycled anode. Gray deposition composed of dendrites and particles was formed on the lower surface of the MCMB layer first, then on the upper surface. The deposition and MCMB layer peeled off from the current collector, and a bump was formed in the cycled anode. The exfoliation and thick deposition increased the ohmic resistance, film resistance, and charge transfer resistance of the cell and decreased the capacity significantly. Metallic lithium did not exist in either the upper or the lower deposition layer according to the results of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), the discharge curve, and anode potential. The outer region of both the lower and the upper deposition layers consisted of Li2CO3, LiOH, ROCO2Li, and ROLi. The inner region of the etched lower deposition layer mainly consisted of Li2O, LiF, and Li2CO3, and that of the etched upper deposition layer mainly consisted of Li2CO3, ROCO2Li, ROLi, and LiF. Solid electrolyte interphase (SEI) film hindering the intercalation of lithium ions into carbon layers and LiCoO2 cathode providing lithium source for the deposition were the two reasons leading to the formation of lithium compound deposition during long-term cycles. Because SEI film on the lower surface of MCMB layer was thicker than that on the upper surface, lithium compound deposition generated on the lower surface first.

Recovery Strategy and Mechanism of Aged Lithium Ion Batteries after Shallow Depth of Discharge at Elevated Temperature.

Performance degradation of prismatic lithium ion batteries (LIBs) with LiCoO2 and mesocarbon microbead as active materials is investigated at an elevated temperature for shallow depth of discharge. Aged LIBs are disassembled to characterize the interface morphology, bulk structure, and reversible capacity of an individual electrode. It is found that the formation of interfacial blocking layer (IBL) on the anode results in the cathode state of charge (SOC) offset, which is the primary reason for the cathode degradation. The main capacity degradation of the anode is attributed to the IBL on the anode surface that impedes the intercalation and deintercalation of lithium ions. Because the full battery capacity is limited by the cathode during aging, the cathode SOC offset is the most important reason for the full battery capacity loss. Interestingly, the capacity of aged LIBs can be recovered to a relative high level after adding the electrolyte, rather than the solvent. This recovery is attributed to the relief of the cathode SOC offset and the dissolution of the anode IBL, which reopens the intercalation and deintercalation paths of lithium ions on the anode. Moreover, it is revealed that the relief of cathode SOC offset and the dissolution of anode IBL trigger and promote mutually to drive the recovery of LIBs.