Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

• Published in: Journal of the Electrochemical Society 2017-01, Vol.164 (2), p.A389-A399
• Main Authors: Gilbert, James A., Shkrob, Ilya A., Abraham, Daniel P.
• Format: Article
• Language: English
• Subjects: electrochemistry; ENERGY STORAGE; graphite; high voltage; layered oxides; manganese; NCA; NCM523 oxide; nickel; SEI
• ISSN: 0013-4651; 1945-7111
• DOI: 10.1149/2.1111702jes

Continuous operation of full cells with layered transition metal (TM) oxide positive electrodes (NCM523) leads to dissolution of TM ions and their migration and incorporation into the solid electrolyte interphase (SEI) of the graphite-based negative electrode. These processes correlate with cell capacity fade and accelerate markedly as the upper cutoff voltage (UCV) exceeds 4.30 V. At voltages ≥4.4 V there is enhanced fracture of the oxide during cycling that creates new surfaces and causes increased solvent oxidation and TM dissolution. Despite this deterioration, cell capacity fade still mainly results from lithium loss in the negative electrode SEI. Among TMs, Mn content in the SEI shows a better correlation with cell capacity loss than Co and Ni contents. As Mn ions become incorporated into the SEI, the kinetics of lithium trapping change from power to linear at the higher UCVs, indicating a large effect of these ions on SEI growth and implicating (electro)catalytic reactions. We estimate that each MnII ion deposited in the SEI causes trapping of ∼102 additional Li+ ions thereby hastening the depletion of cyclable lithium ions. Using these results, we sketch a mechanism for cell capacity fade, emphasizing the conceptual picture over the chemical detail.