Extensive Migration of Ni and Mn by Lithiation of Ordered LiMg0.1Ni0.4Mn1.5O4 Spinel
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- 作者：Marnix Wagemaker ; Frans G. B. Ooms ; Erik M. Kelder ; Joop Schoonman ; Gordon J. Kearley ; Fokko M. Mulder ; and F.M. Mulder
- 刊名：Journal of the American Chemical Society
- 出版年：2004
- 出版时间：October 20, 2004
- 年：2004
- 卷：126
- 期：41
- 页码：13526 - 13533
- 全文大小：265K
- 年卷期：v.126,no.41(October 20, 2004)
- ISSN：1520-5126
文摘
LixMg0.1Ni0.4Mn1.5O4 spinel (P4332) was chemically and electrochemically lithiated in the range 1< x 
2.25 and subjected to detailed X-ray and neutron diffraction analysis to understand the electrochemicalbehavior in the 3 V region. Extensive migration of Ni and Mn during lithium insertion was found, resultingin the disappearance of the initial Ni-Mn ordering and the formation of Ni-rich and Ni-poor domains, leadingto two Jahn-Teller-distorted tetragonal phases with different Ni:Mn ratios. Such extensive Ni and Mnmigration was not known for these spinels, and strongly influences the initial cycling behavior. The newlyformed tetragonal phase with a Ni:Mn ratio of ~0.07 has a higher cyclability and a higher capacity, and istherefore suggested to have a favorable composition for this intercalation range, as is confirmed in theliterature. In addition, lithium is found to occupy multiple positions inside the distorted oxygen octahedronof this phase, a finding previously known only for lithium in anatase TiO2.
2.25 and subjected to detailed X-ray and neutron diffraction analysis to understand the electrochemicalbehavior in the 3 V region. Extensive migration of Ni and Mn during lithium insertion was found, resultingin the disappearance of the initial Ni-Mn ordering and the formation of Ni-rich and Ni-poor domains, leadingto two Jahn-Teller-distorted tetragonal phases with different Ni:Mn ratios. Such extensive Ni and Mnmigration was not known for these spinels, and strongly influences the initial cycling behavior. The newlyformed tetragonal phase with a Ni:Mn ratio of ~0.07 has a higher cyclability and a higher capacity, and istherefore suggested to have a favorable composition for this intercalation range, as is confirmed in theliterature. In addition, lithium is found to occupy multiple positions inside the distorted oxygen octahedronof this phase, a finding previously known only for lithium in anatase TiO2.