Strain Evolution in Lithium Manganese Oxide Electrodes
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Lithium manganese oxide, LiMn2O4 (LMO) is a promising cathode material, but is hampered by significant capacity fade due to instability of the electrode-electrolyte interface, manganese dissolution into the electrolyte and subsequent mechanical degradation of the electrode. In this work, electrochemically-induced strains in composite LMO electrodes are measured using the digital image correlation (DIC) technique and compared with electrochemical impedance spectroscopy (EIS) measurements of surface resistance for different scan rates. Distinct, irreversible strain variations are observed during the first delithiation cycle. The changes in strain and surface resistance are highly sensitive to the electrochemical changes occurring during the first cycle and correlate with prior reports of the removal of the native surface layer and the formation of cathode-electrolyte interface layer on the electrode surface. A large capacity fade is observed with increasing cycle number at high scan rates. Interestingly, the total capacity fade scales proportionately to the strain generated after each lithiation and delithiation cycle. The simultaneous reduction in capacity and strain is attributed to chemo-mechanical degradation of the electrode. The in situ strain measurements provide new insight into the electrochemical-induced volumetric changes in LMO electrodes with progressing cycling and may provide guidance for materials-based strategies to reduce strain and capacity fade.
KeywordsCathode-electrolyte Interface Strain measurement Lithium manganese oxide Deformation Surface reactions
This work was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U. S. Department of Energy, Office of Science, Basic Energy Sciences. The authors would like to acknowledge the Beckman Institute for Advanced Science and Technology for use of microscopy equipment and Dr. Joseph Lyding for use of spot welding equipment.
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