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

2017· article· en· 485 citations· W2569358455 on OpenAlex· 10.1149/2.1111702jes

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Opus teacher head0.008
GPT teacher head0.222
Teacher spread
0.214 · how far apart the two teachers sit on this one work
Validation status
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

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. Lastly, we estimate that each Mn<sup>II</sup> ion deposited in the SEI causes trapping of ~10<sup>2</sup> additional Li<sup>+</sup> 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.

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The record

Venue
Journal of The Electrochemical Society
Topic
Advancements in Battery Materials
Field
Engineering
Canadian institutions
Funders
Argonne National LaboratoryBasic Energy SciencesDalhousie UniversityOffice of ScienceUniversity of ChicagoU.S. Department of Energy
Keywords
DissolutionCapacity lossElectrolyteLithium (medication)IonOxideTransition metalFadeElectrodeChemistryInterphaseMaterials scienceInorganic chemistryChemical engineeringCatalysisPhysical chemistry
Has abstract in OpenAlex
yes