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Synthesis of Metal-Substituted Manganese Dioxides by Soft-Chemistry Method and Application to Active Electrode Materials in secondary cells

软化学法合成金属取代二氧化锰及其在二次电池活性电极材料中的应用

基本信息

批准号：
15350117
负责人：
KUMAGAI Naoaki
金额：
$ 7.62万
依托单位：
Iwate University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2006
项目状态：
已结题

项目摘要

The present research has aimed to synthesis several metal-substituted manganese dioxides by soft-chemistry routes, such as aqueous solution, hydrothermal, emulsion drying, and spray-drying methods. The chemical compositions and crystal structures of the prepared manganese dioxides were examined, and furthermore the electrochemical characteristics of the prepared manganese oxides were investigated as new cathode materials for secondary lithium batteries. The main results were as follows.1.New hollandite-type Co-doped α-K_<0.12>(Mn_<1-x>Co_x)O_2 (x=0〜0.12) and orthorhombic LiMn_<1-x>M_x,O_2 (O<x≦0.14 in M=Co,O<x0.1.5 in M=Fe) have been synthesized by aqueous solution and hydrothermal methods, respectively. The crystal structure, surface fine structure, structural variation with lithium intercalation, and lithium diffusion behavior in the crystal lattice were examined.2.The layered Li excess Li_<1+x>Ni_<0.5>Mn_<0.5>O_2 and its Ti-substituted LiNi_<0.5>Mn_<0.5-x>Ti_xO_2 (x=0〜0.3) have been synthesized by an emulsion-drying method. The structural analysis of the prepared layered materials was carried out by X-ray diffraction, newtron diffraction and X-ray absorption spectroscopic methods. These prepared materials showed a high discharge capacity of 170〜180 mAh/g oxide during 50 cyclings.3.The layered Li_<1-x>(Ni_<1/3>Co_<1/3>Mn_<1/3>)_xO_2(0≦x≦0.17) has been prepared by a spray-drying method, and the electrochemical characteristics and structural stability have been investigated. The crystal lattice parameter decreased with increasing the amount of Li excess (x-value), and at x=0.17 the highest discharge capacity of 179 mAh/g was obtained during 50 cyclings, due to the enhanced structural stability

本研究旨在通过水溶液法、水热法、乳化干燥法和喷雾干燥法等软化学方法合成几种金属取代的二氧化锰。对所制备的二氧化锰的化学组成和晶体结构进行了分析，并对所制备的二氧化锰作为新型锂离子电池正极材料的电化学性能进行了研究。1.分别采用水溶液法和水热法合成了新的钴掺杂的奥氏体型α-K_<0.12>（Mn_<1-x>Co_x）O_2（x=0 ~ 0.12）和正交晶系LiMn<1-x>_x，O_2（M=Co时O<x <0.14，M=Fe时O<x <0.1.5）。2.采用乳液干燥法合成了层状Li过量Li_（1+x）Ni_<0.5>Mn_xO_2<0.5>及其Ti取代的Li Ni_<0.5>Mn_xTi_xO_2<0.5-x>（x=0 ~ 0.3）。用X射线衍射、牛顿衍射和X射线吸收光谱等方法对所制备的层状材料进行了结构分析。采用<1-x>喷雾干燥法制备了层状Li_（Ni_<1/3>Co_<1/3>Mn_<1/3>）_xO_2（0 × 10 ~（-1）× 0.17），并对其电化学性能和结构稳定性进行了研究。随着Li过量量（x值）的增加，晶格常数减小，在x=0.17时，由于结构稳定性的增强，在50次循环中获得了179 mAh/g的最高放电容量