Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 16, Issue 28, Pages 14665-14668Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4cp01799d
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Funding
- Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. DOE under the Batteries for Advanced Transportation Technologies (BATT) Program [DE-AC02-05CH11231, 7056412]
- National Science Foundation [OCI-1053575]
- ORNL's Center for Nanophase Materials Sciences (CNMS)
- Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy
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A novel oxygen vacancy assisted transition metal (TM) diffusion mechanism is proposed for the first time to explain the near-surface phase transformation in lithium excess transition metal layered oxides. Oxygen vacancies and TM migration have been observed at nm scale spatial resolution by Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy. Formation of (dilute) oxygen vacancies and their roles in assisting transition metal ion diffusion were further investigated using first principles calculations. The activation barriers of TM diffusion in the presence of oxygen vacancies are drastically reduced and consistently in a reasonable range for room temperature diffusion.
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