成果報告書詳細
管理番号20140000000205
タイトル*平成25年度中間年報 革新型蓄電池先端科学基礎研究事業 革新型蓄電池先端科学基礎研究開発 (8)
公開日2014/6/11
報告書年度2013 - 2013
委託先名国立大学法人東京工業大学
プロジェクト番号P09012
部署名スマートコミュニティ部
和文要約
英文要約In this fiscal year, we developed the materials and experimental techniques as the material innovation group subject and the advanced analysis group subject. The lithium-excess layered rock-salt materials (Lix(Mn, Co, Ni)0.8O2: x > 1.2) were developed using high-pressure and a pulsed laser deposition methods, and their structures, compositions, oxidation states of transition metals were clarified. The ICP measurements for Lix(Mn, Co, Ni)0.8O2 confirmed that the lithium content in the crystals increased with increasing excess oxygen content during the synthesis process. X-ray absorption measurements revealed that the larger amount of excess oxygen made higher oxidation state of the transition metals. The excess lithium occupies the tetrahedral site in the crystal structure. Cycling characteristics were improved with the increase in the excess oxygen content. The oxygen pressure was found to affect the crystal structure, charge-discharge characteristics, oxidation state of transition metals and lithium content. Fluorine substitution of Lix(Mn, Co, Ni)0.8O2 was examined. However, the present synthesis condition could not provide the layered phase and further optimization of the synthesis conditions is necessary. The Li2MnO3 epitaxial thin films with the (001) orientation and a thickness of 20 - 30 nm were synthesized on the SrTiO3(111) substrates. The epitaxial films had small surface roughness (< 2 nm), which might provide a suitable reaction field for the interfacial reaction analysis. The epitaxial thin films showed superior charge-discharge characteristics. In situ XRD measurements clarified that the thin films showed large structural changes during the first discharge process and the small crystallite size contributes to their superior cycling characteristics. In situ X-ray reflectometry using molybdenum X-ray source was developed for the mechanistic study on the interfacial reactions of thin film electrodes. Kissing-fringes were successfully observed during the battery operation using the in situ cell. A 18650-type lithium secondary batteries were subjected to in situ neutron diffraction measurements. The structural changes of both anode and cathode were observed using the beamline BL09 and SPICA diffractometer. Novel analysis system and the software were developed to deal with large amount of the diffraction data.
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