期刊
CHEMISTRY OF MATERIALS
卷 20, 期 24, 页码 7454-7464出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm802316d
关键词
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资金
- U.S. Department of Energy, Office of FreedomCAR and Vehicle Technologies
- Lawrence Berkeley National Laboratory
- National Science Foundation [DMR 0705657]
The structural and physical properties of the low cobalt material, LiNi0.45Mn0.45Co0.1O2, have been investigated. Nearly stoichiometric LiNi0.45Mn0.45Co0.1O2 with the optimal electrochemical performance was produced at 800 degrees C by coprecipitation method. A higher synthesis temperature leads to a higher crystallinity and larger particles not influencing the Ni/Li disorder. Nonstoichiometric Li1+z(Ni0.45Mn0.45Co0.1)(1-z)O-2, 0.8 <= 1 + z <= 1.2, were then studied; it was found that the interslab Ni content increases as the lithium content decreases. However, the lithium content in the metal layer decreases simultaneously minimizing the formation of tetrahedral lithium upon charging. As a result, the Li-deficient Li-0.9(Ni0.45Mn0.45Co0.1)(1.1)O-2 has the best electrochemical capacity (190 mAh/g between 2.5 and 4.6 V at 0.5 mA/cm(2)) and cycleability. The electrochemical performance is compared to that of other well-studied Li(NiyMnyCo1-2y)O-2 materials with y = 1/3, 0.4, 0.425, and 0.5. The magnetism of Li1+z(Ni0.45Mn0.45Co0.1)(1-z)O-2 studied in conjunction with the structure is dominated by the ordering of interlayer and intralayer ferrimagnetic clusters. The interlayer clusters nucleate at interslab Ni2+ ions and their size increases with the Ni/Li disorder, while the intralayer clusters size increases in materials with larger particle size and smaller amount nonmagnetic ions in the transition metal layers. This model allows using magnetism to estimate the character of the transition metal ordering.
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