期刊
CHEMISTRY OF MATERIALS
卷 27, 期 22, 页码 7729-7733出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.5b03360
关键词
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资金
- National Science Foundation Materials Interdisciplinary Research Team (MIRT) grant [DMR-1122603]
- Welch Foundation [F-1254]
- Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
The thermal conversion of chemically delithiated layered Li0.5Ni1-yMnyO2 (0.2 <= y <= 0.5) into spinel-like LiNi2-yMnyO4 (0.4 <= y <= 1) has been systematically investigated. The formed spinel-like phases are metastable and cannot be accessed by a conventional high-temperature solid-state method. The layered-to-spinel transformation mechanism has been studied by the Rietveld refinement of in situ neutron diffraction as a function of temperature (25-300 degrees C). In particular, the ionic diffusion of Li and M ions is quantified at different temperatures. Electrochemistry of the metastable spinel-like phases obtained has been studied in lithium-ion cells. A bond valence sum map has been performed to understand the ionic diffusion of lithium ions in the Ni-rich layered, spinel, and rock-salt structures. The study can aid the understanding of the possible phases that could be formed during the cycling of Ni-rich layered oxide cathodes.
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