期刊
ADVANCED ENERGY MATERIALS
卷 4, 期 13, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/aenm.201301453
关键词
manganese oxide; layered oxides; lithium batteries; sodium batteries; electrodes
类别
资金
- JSPS
- MEXT [24750186]
- Japanese Ministry of Education, Science, Sports and Culture
- Nanotechnology Support Project [2012B1777, 2013A1681]
- Inter-University Research Program on Neutron Scattering of IMSS, KEK
- Ministry of Education Culture, Sports, Science and Technology, Japan
- Grants-in-Aid for Scientific Research [24750186] Funding Source: KAKEN
A new and promising P2-type layered oxide, Na-5/6[Li1/4Mn3/4]O-2 is prepared using a solid-state method. Detailed crystal structures of the sample are analyzed by synchrotron X-ray diffraction combined with high-resolution neutron diffraction. P2-type Na-5/6[Li1/4Mn3/4]O-2 consists of two MeO2 layers with partial in-plane 3a x 3a-type Li/Mn ordering. Na/Li ion-exchange in a molten salt results in a phase transition accompanied with glide of [Li1/4Mn3/4]O-2 layers without the destruction of in-plane cation ordering. P2-type Na-5/6[Li1/4Mn3/4]O-2 translates into an O2-type layered structure with staking faults as the result of ion-exchange. Electrode performance of P2-type Na-5/6[Li1/4Mn3/4]O-2 and O2-type Li-x[Li1/4Mn3/4]O-2 is examined and compared in Na and Li cells, respectively. Both samples show large reversible capacity, ca. 200 mA h g(-1), after charge to high voltage regardless of the difference in charge carriers. Structural analysis suggests that in-plane structural rearrangements, presumably associated with partial oxygen loss, occur in both samples after charge to a high-voltage region. Such structural activation process significantly influences electrode performance of the P2/O2-type phases, similar to O3-type Li2MnO3-based materials. Crystal structures, phase-transition mechanisms, and the possibility of the P2/O2-type phases as high-capacity and long-cycle-life electrode materials with the multi-functionality for both rechargeable Li/Na batteries are discussed in detail.
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