SOLID-STATE IONICS - HIGH COPPER-ION CONDUCTIVITY OF THE SYSTEM CUCL-CUL-RBCL
SOLID-STATE IONICS - HIGH COPPER-ION CONDUCTIVITY OF THE SYSTEM CUCL-CUL-RBCL
复制标题
DOI：
10.1149/1.2128770
复制
发表时间：
1979-01-01
影响因子：
3.9
通讯作者：
HAYASHI, S
中科院分区：
文献类型：
--
作者：
TAKAHASHI, T;YAMAMOTO, O;HAYASHI, S
在CuC 1-CuI-RbC 1体系中发现了一种新的高铜离子电导率固体电解质Rb_4CuIsIzCl_5。该化合物在25 ℃时的铜离子电导率为0.34（2-cm）-i，在130~ 25 ℃和25 ~ 140 ℃之间的电导激活能分别为7.0 kJ/mol和19 kJ/mol。粉末X射线衍射分析表明，Rb~（13）CulsIV_（14）Cl_2的晶体结构为简单立方结构，α = 10.02。在过去的几年中，人们研究了许多以卤化铜（I）为基础的体系的物理化学性质，结果总结在表I中。在卤化铜-取代卤化铵体系中发现了一些高铜离子电导率的固体电解质。溴化铜（I）与二溴化二氢三亚乙基二胺（C_4H_5N_2Br_2）的复盐在25 ℃时电导率最高，为0.065（~-cm）-Z。布拉德利和格林报道了CuI-KI和CuI-RbI体系的相图（1），并发现KCu_4 I ~-在257 ~ 332 ℃范围内存在。Bonino和Lazzari测得KCu_4 I ~-在270 ℃时电导率为0.6（~-cm）~（-1）（4）。利用高温电导率数据外推到室温的电导率约为0.1（~ 2-cm）-1。然而，KCuj 5在低于257 ° C下分解为CuI和KI，并且在室温下表现出差的导电性。最近，Matsui和瓦格纳报道了CuCl-RbCl体系在25~ 75摩尔%（m/o）CuCl（6）下具有2.5 × 10- 5（~-cm）-I的相对高的铜离子电导率。最近，Takahashi和Yamamoto（8）研究了CuX-RX系统的相图和电导率，其中X是Cl、Br或I，R是K、Rb或Cs。在这些体系中，除KCu_4 I ~-外，没有发现MCu_4X_5型的中间化合物。的
A new high copper ion conductivity solid electrolyte Rb4CuIsIzClls has been found in the CuC1-CuI-RbC1 system. This compound has a copper ion conductivity of 0.34 (2-cm)-i at 25 C, and activation energies for conduction of 7.0 kJ/mole between 130~ and--25~ and 19 kJ/mole between--25~ and--140~ respectively. Powder x-ray diffraction analysis indicates that the crystal structure of Rb~ CulsIvClia is simple cubic with a: 10.02 A.During the past several years, manysystems based on copper (I) halides have been studied as to their physico-chemical properties and the results are summarized in Table I. Some high copper ion conductivity solid electrolytes have been found in the systems copper (I) halides-substituted ammonium halides. The highest conductivity of 0.065 (~-cm)-Z was found at 25~ in the double salt of copper (I) bromide and N, N'-dihydro-triethylenediamine dibromide (C4HsN2Br2). Bradley and Greene reported the phase diagrams of the systems CuI-KI and CuI-RbI (1), and KCu4I~ was found in the temperature range between 257 and 332~ Tl~ e electrical conductivity of KCu4I~ was measured to be 0.6 (~-cm)-1 at 270~ by Bonino and Lazzari (4). The conductivity extrapolated to room temperature by using the high temperature conductivity data is about 0.1 (~ 2-cm)-1. However, KCuj5 decomposes to CuI and KI below 257~ and exhibits a poor conductivity at room temperature. Recently, the CuC1-RbC1 system was reported by Matsui and Wagner to have a relatively high copper ion conductivity of 2.5 X 10-s (~-cm)-I at 25~ at 75 mole percent (m/o) CuCI (6). More recently, the phase diagrams and the electrical conductivities of the systems CuX-RX, where X is C1, Br, or I and R is K, Rb, or Cs, have been examined by Takahashi and Yamamoto (8). No intermediate compound of the type MCu4X5 was found in these systems, except for KCu4I~. The