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Synthesis of Iithium ion conductors with an average structure

具有平均结构的锂离子导体的合成

基本信息

批准号：
08455405
负责人：
SATO Mineo
金额：
$ 0.32万
依托单位：
NIIGATA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455405/
关键词：
Lithium ionic conductor Phase transition Superionic conductor Solid state reaction Lithium ion battery Cathode material ゾルゲル法イオン伝導体金属アルコキシド薄膜

项目摘要

The present study has been aimed to obtain fundamental aspects on the design for a room temperature superionic conducting material, Li_3M_2 (PO_4)_3 (M=Sc and In), which has a so called average structure at a high temperature. In order to obtain the superionic conducting phase Li_3M_2 (PO_4)_3 (M=Sc and In), several kinds of aliovalent ions such as Mg^<2+>, Ti^<4+>, Zr^<4+>, Sn^<4+>, Hf^<4+>, Nb^<5+>, and Ta^<5+> were substituted for the M site. The differential thermal analysis indicated that no phase transition existed in the divalent ion substituted samples with the substituted ratio over 5 mol%, the tetravalent ion substituted samples with the ratio over 5 mol%, and the pentavalent ion substituted samples with the ratio over 2.5 mol%. The highest ionic conducting materials, which were found in the Ti-and Zr-substituted samples, has a quite higher room temperature conductivity by three orders of magnitude than that of the unsubstituted samples. The neutron diffraction measurements confirmed the stabilization of the high temperature phase at room temperature in the substituted samples, and also confirmed a disorder of Li ion distribution among three kinds of available sites, giving a driving factor to the stabilization of the high temperature phase. The substituted materials could be a promising material for the solid electrolyte in a solid state lithium battery or a chemical sensor.We also investigated the stabilization of the high temperature phase of Li_3V_2 (PO_4)_3, which has the same structure as that of Li_3M_2 (PO_4)_3. The stabilization of the high temperature phase was also observed in this compound by substituting 10 mol% of Zr for M sites. The charge-discharge capacity of an electrochemical lithium cell where this material was used as a cathode material was found to be improved by 20%.

本研究的目的是为高温下具有所谓平均结构的室温超离子导电材料Li_3M_2（PO_4）_3（M=Sc和In）的设计提供基础。为了获得超离子导电相Li_3M_2（PO_4）_3（M=Sc和In），用Mg^<2+>、Ti^<4+>、Zr^<4 +>、Sn^<4 +>、Hf^<4 +>、Nb^<5+>和Ta^<5+>等离子取代M位。差热分析表明，取代率大于5mol%的二价离子取代样品、取代率大于5mol%的四价离子取代样品和取代率大于2.5mol%的五价离子取代样品均不存在相变。最高的离子导电材料，这是在Ti和Zr取代的样品中发现的，具有相当高的室温电导率的三个数量级比未取代的样品。中子衍射测量证实了高温相在室温下的稳定性，在替代样品中，也证实了无序的锂离子分布在三种可用的网站，给一个驱动因素的高温相的稳定。本文还研究了与Li_3M_2（PO_4）_3结构相同的Li_3V_2（PO_4）_3高温相的稳定性。在该化合物中，通过用10摩尔%的Zr取代M位点，也观察到高温相的稳定化。发现将该材料用作阴极材料的电化学锂电池的充放电容量提高了20%。