New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries

被引：477

作者：

Yabuuchi, Naoaki ^{[1
,2
]}

Hara, Ryo ^{[1
]}

Kajiyama, Masataka ^{[1
]}

Kubota, Kei ^{[1
]}

Ishigaki, Toru ^{[3
]}

Hoshikawa, Akinori ^{[3
]}

Komaba, Shinichi ^{[1
,2
]}

机构：

[1] Tokyo Univ Sci, Dept Appl Chem, Shinjuku Ku, Tokyo 1628601, Japan

[2] Kyoto Univ, Elements Strategy Initiat Catalysts & Batteries, Kyoto 6158520, Japan

[3] Ibaraki Univ, Frontier Res Ctr Appl Atom Sci, Tokai, Ibaraki, Japan

来源：

ADVANCED ENERGY MATERIALS | 2014年 / 4卷 / 13期

关键词：

manganese oxide; layered oxides; lithium batteries; sodium batteries; electrodes; X-RAY-DIFFRACTION; POSITIVE ELECTRODE; ELECTROCHEMICAL CHARACTERIZATION; CATHODE MATERIALS; CRYSTAL-STRUCTURE; ION BATTERIES; METAL-OXIDES; SODIUM-ION; LITHIUM; NA;

D O I：

10.1002/aenm.201301453

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070305 [高分子化学与物理];

摘要：

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.

引用

页数：23

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