Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells
Open Access
- 22 December 2016
- journal article
- Published by The Electrochemical Society in Journal of the Electrochemical Society
- Vol. 164 (2), A389-A399
- https://doi.org/10.1149/2.1111702jes
Abstract
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.Funding Information
- U.S. Department of Energy (Department of Energy) (DE-AC02-06CH11357)
This publication has 79 references indexed in Scilit:
- Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approachesMaterials Science and Engineering B, 2015
- Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy DensityJournal of the Electrochemical Society, 2013
- Understanding the Degradation Mechanisms of LiNi0.5Co0.2Mn0.3O2 Cathode Material in Lithium Ion BatteriesAdvanced Energy Materials, 2013
- Li+-solvation/desolvation dictates interphasial processes on graphitic anode in Li ion cellsJournal of Materials Research, 2012
- Recent progress in cathode materials research for advanced lithium ion batteriesMaterials Science and Engineering: R: Reports, 2012
- A review of the features and analyses of the solid electrolyte interphase in Li-ion batteriesElectrochimica Acta, 2010
- Building better batteriesNature, 2008
- Issues and challenges facing rechargeable lithium batteriesNature, 2001
- Layered Lithium Insertion Material of LiNi1/2Mn1/2O2 : A Possible Alternative to LiCoO2 for Advanced Lithium-Ion BatteriesChemistry Letters, 2001
- Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion BatteriesElectrochemical and Solid-State Letters, 2001