液相法によるリチウムイオン伝導性酸化物の低温合成

液相法低温合成锂离子导电氧化物

• 批准号: 13F03371
• 负责人: 忠永 清治
• 金额: $ 1.47万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2013
• 资助国家: 日本
• 起止时间: 2013-04-01 至 2016-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13F03371/
• 关键词: 固体電解質; リチウム電池; ゾル－ゲル法; 低温合成; リチウムイオン電池; ゾルーゲル法

Lithium garnet-type oxides Li7-xLa3Zr2-xNbxO12 (LLZNbO, x=0-1) were prepared by a sol-gel process at low temperatures. Then, glass additives, LiO2-B2O3-SiO2 glass and BaO-B2O3-SiO2 glass, were used to stimulate the sintering of the ceramic electrolyte retaining the cubic phase stable at low temperatures.The cubic garnet phase was formed by a heat-treatment of sol-gel derived precursor powders at 600 - 700 degree C. The presursor powders and glass additives, 53LiO2･31B2O3･12SiO2 (mol%) (LiO2-B2O3-SiO2 glass) or 35BaO･10CaO･5Al2O3･15B2O3･10SiO2 (mol%) (BaO-B2O3-SiO2 glass) were pressed into pellets and sintered at 900 degree C.The relatative density of 86% was achieved by the sintering with glass additives at 900 degree C. In the composites sintered with the BaO-B2O3-SiO2 glass, the presence of La2Zr2O7 was detected at concentration higher of 4 wt%, while the single cubic phase was obtained for the composites sintered with the LiO2-B2O3-SiO2 glass.The ionic conductivity of the obtained composite was 8x10^-5 S/cm at 30 degree C using 4 wt.% of LiO2-B2O3-SiO2 glass. The conductivity is 20% lower than the material reported by the solid state reaction process, but the heat treatment used is about 300 degree C lower than that required by the conventional solid state reaction process. This represents an important contribution to further application of the LLZNbO solid electlolyte to all-solid-state battery.

采用溶胶-凝胶法在低温下制备了锂石榴石型氧化物Li7-xLa3Zr2-xNbxO12（LLZNbO，x=0-1），然后加入玻璃添加剂LiO2-B2O3-SiO2玻璃和BaO-B2O3-SiO2玻璃，用于刺激陶瓷电解质的烧结，从而在低温下保持立方相稳定。立方石榴石相是通过在 600 - 700 摄氏度下对溶胶-凝胶衍生的前体粉末进行热处理而形成的。前体粉末和玻璃添加剂为 53LiO2･31B2O3･12SiO2 (mol%)（LiO2-B2O3-SiO2 玻璃）或 35BaO･10CaO ･5Al2O3･15B2O3･10SiO2 (摩尔%)将BaO-B2O3-SiO2玻璃制成颗粒并在900℃下烧结。通过在900℃下添加玻璃添加剂进行烧结，相对密度达到86%。在用BaO-B2O3-SiO2玻璃烧结的复合材料中，在浓度高于 4 wt% 时检测到 La2Zr2O7 的存在，同时复合材料获得了单一立方相与LiO2-B2O3-SiO2玻璃一起烧结。使用4wt.%的LiO2-B2O3-SiO2玻璃得到的复合材料的离子电导率在30℃下为8x10^-5 S/cm，电导率比原来的低20%。该材料是采用固相反应工艺报道的，但所用的热处理温度比传统固相反应工艺所需的温度低约300℃，这是一个重要的成果。为LLZNbO固体电解质在全固态电池中的进一步应用做出贡献。

项目成果

Institute of Ceramics and Glass, CSIC(Spain)

中船重工陶瓷玻璃研究所（西班牙）

Effect of glass additives on relative dnesity and Li-ion conductivity of Li7-xLa3Zr2-xNbxO12 solid electrolyte

玻璃添加剂对Li7-xLa3Zr2-xNbxO12固体电解质相对密度和锂离子电导率的影响

• 发表时间: 2015
• 作者: N.C. Rosero Navarro;T. Yamashita;A. Miura;M. Higuchi;K. Tadanaga
• 通讯作者: K. Tadanaga

ゾルゲル法によるLi_7La_3(Zr_<2-x>Nb_x)O_<12>の低温合成

溶胶-凝胶法低温合成Li_7La_3(Zr_<2-x>Nb_x)O_<12>

• 发表时间: 2014
• 作者: 山下平;Carorina Resero;樋口幹雄;忠永清治
• 通讯作者: 忠永清治

Sol-gel synthesis of Li7-xLa3Zr2-xNbxO12 solid electrolyte at low temperature. Effect of glass additives on relative density and Li-ion conductivity

低温溶胶-凝胶合成Li7-xLa3Zr2-xNbxO12固体电解质。

• 发表时间: 2015
• 作者: N. C. Rosero Navarro;T. Yamashita;A. Miura;M. Higuchi;K. Tadanaga
• 通讯作者: K. Tadanaga

Low temperature sintering of sol-gel derived Li7-xLa3Zr2-xNbxO12 solid electrolyte by using sintering additives

使用烧结添加剂低温烧结溶胶-凝胶衍生的Li7-xLa3Zr2-xNbxO12固体电解质

• 发表时间: 2016
• 作者: Nataly Carolina Rosero Navarro;Taira Yamashita;Akira Miura;Mikio Higuchi and Kiyoharu Tadanaga
• 通讯作者: Mikio Higuchi and Kiyoharu Tadanaga