期刊
CHEMISTRY OF MATERIALS
卷 19, 期 5, 页码 1016-1023出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm0621747
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The conversion upon electrochemical cycling from a layered structure to a spinel in nonstoichiometric LixMnyO2 has been studied by neutron diffraction and NMR. This process occurs in all layered lithium manganate materials, irrespective of the ion-exchange route. The high temperature of the ion exchange under reflux in n-hexanol is sufficient to promote formation of some spinel within the as-synthesized material. Upon cycling, all the different layered LixMnyO2 compounds begin to transform to a spinel. In the first 50 or so cycles, the various layered LixMnyO2 compounds behave rather differently, with a higher spinel fraction being observed for materials ion-exchanged under more extreme conditions. However, the rate of this transformation is significantly slower than was observed in stoichiometric layered LiMnO2, with only 25% spinel observed after 100 cycles. Ultimately, upon extended cycling, the entire structure will form a well-ordered spinel phase.
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