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Preparation and Characterization of Perovskite-type ternary Sulfides.

钙钛矿型三元硫化物的制备和表征。

基本信息

批准号：
05650632
负责人：
UCHIDA Takashi
金额：
$ 1.41万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

Some of the ternary oxides having Perovskite-type structure, ABO_3 (A,B : metals), orrelatcd compounds exhibit interesting electuic, dielectric and/or magnetic properties, e.g., BaTiO_3, YBa_2Cu_3O_y. However, only a few termary sulfides having Perovskite-type structure have been known, so far although, several interesting possibitities, such as cathde materiasls of lithium secondary batteries can be expected for these compounds. Accordingly, I have tried to prepare Perovskite-type ternary sulfides in this study.In 1993, preparatios of LiMnS_3, LiWS_3, LiCrS_3, CuMnS_3, CuWS_3, CuCrS_3 Perovskites were carried out using each metal element, Li_2S and sulfur, in evacuated quartz tubes at temperatures of 600-800ﾟC.However, in each case excess sulfur was left in the quartz tube, and no perovskites were obtained. Accordingly, in 1994, ternary sulfides with lower sulfur compositions were prepared. In the Cu-Cr-S system, CuCr_2S_4 spinel was prepared. From this compound, some part of copper ions was rcmoved by a leaching reaction using hydrochloric acid, which could be used as a cathode material of a lithium secondary battery, and the lithium cell showed an energy density of 50 Wh/kg. In the Li-Mn-S system, a new compound, which is supposed to be the LiMn_2S_4 spinel, was obtained(no single phase was obtained). The cathode property of this material is going to be tested. In this system, Li_xMn_<1-x>S with a cubic NaCl type structure was also preparcd. The homogeniety range of this solid solution was found to be 0<x<0.27. The lattice parameter of cubic MnS decreased with increasing x value. Also, the specific resistivity of MnS(-10^<-6>OMEGA ・ cm, 20ﾟC)decreased to -10^<-2>OMEGA ・ cm for Li_<0.2>Mn_<0.8>. Li_xMn_<1-x>S is also a new compound, and characterizations are going to be carried out.

一些具有钙钛矿型结构的三元氧化物，ABO_3 （A，B：金属），或相关化合物表现出有趣的电学，介电和/或磁性能，如BaTiO_3， YBa_2Cu_3O_y。然而，到目前为止，只有少数具有钙钛矿型结构的三元硫化物被发现，尽管有几种有趣的可能性，例如锂二次电池的阴极材料可以期待这些化合物。因此，我在本研究中尝试制备钙钛矿型三元硫化物。1993年，在真空石英管中，以Li_2S和硫为原料，分别制备了LiMnS_3、LiWS_3、LiCrS_3、CuMnS_3、CuWS_3、CuCrS_3钙钛矿。然而，在每种情况下，过量的硫留在石英管中，没有钙钛矿得到。因此，在1994年，制备了低硫组成的三元硫化物。在Cu-Cr-S体系中制备了CuCr_2S_4尖晶石。该化合物经盐酸浸出反应除去部分铜离子，可作为锂二次电池正极材料，锂电池的能量密度可达50 Wh/kg。在Li-Mn-S体系中，得到了一种新的化合物，推测其为LiMn_2S_4尖晶石（未得到单相）。这种材料的阴极性能将被测试。在该体系中还制备了具有立方NaCl型结构的Li_xMn_<1-x>S。该固溶体的均匀性范围为0<x<0.27。三次MnS的晶格参数随x值的增大而减小。此外，当Li_<0.2>Mn_<0.8>时，MnS（-10^<-6> ω·cm, 20 C）的比电阻率降至-10^<-2> ω·cm。Li_xMn_<1-x>S也是一个新化合物，并将进行表征。