Journal
ACS NANO
Volume 13, Issue 7, Pages 7825-7832Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.9b02007
Keywords
battery; reflectivity; reflectometry; nucleation; interfaces
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Funding
- Center for Electrochemical Energy Science, an Energy Frontier Research Centre - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11]
- U.S. DOE [DE-AC02-06CH11357]
- MRSEC under National Science Foundation [DMR-1720139]
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Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li2O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.
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