Journal
ADVANCED ENERGY MATERIALS
Volume 7, Issue 7, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.201601778
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Funding
- Center for Electrochemical Energy Science, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences
- National Science Foundation Graduate Research Fellowship Program [DGE-1144245]
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In situ strain and stress measurements are performed on composite electrodes to monitor potential-dependent stiffness changes in lithium manganese oxide (LiMn2O4). Lithium insertion and removal results in asynchronous strain and stress generation in the electrode. Electrochemical stiffness changes are calculated by combining coordinated stress and strain measurements. The electrode experiences dramatic changes in electrochemical stiffness due to potential-dependent Li+ ion intercalation mechanisms. The development of stress in the early stages of delithiation (at approximate to 3.95 V) due to a kinetic barrier at the electrode surface gives rise to stiffness changes in the electrode. Strain generation due to phase transformations reduces stiffness in the electrode at 4.17 V during delithiation and at 4.11 V during lithiation. During lithiation, stress generation due to Coulombic repulsions between occupied and incoming Li+ ions leads to stiffening of the electrode at 3.96 V. The electrode also experiences greater changes in stiffness during delithiation compared to lithiation. These changes in electrochemical stiffness provide insight into the interplay between mechanical and electrochemical properties which control electrode response to lithiation and delithiation.
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