Development of Multivalent Cation Conductive Solid Electrolytes and Their Application to Electrochemical Devices.

关于无机固体电解质的研究已经有很多。近年来，聚合物固体电解质因其具有良好的柔韧性和制造轻薄器件的能力而受到人们的广泛关注。然而，对多价阳离子导电固体电解质的研究却很少。在这项研究中，多价阳离子，如锌或镁，无机和有机类型的导电固体电解质进行了研究。本文首先用频散分析法研究了磷酸锆骨架固体电解质M^Zr_2（PO_4）_3、<II>M^Zr_4（PO_4）_6和M^Zr_6<III>（PO_4）_9的导电机理。以MgZr_4（PO_4）_6 [MgZP]和Na_2CO_3为原料，制备了全固态CO_2气敏元件，并研究了其响应特性。用Si部分取代MgZP制备的CO_2传感器性能优于MgZP。通过电导率测定和XRD分析，研究了Ti部分取代Zr的MgZP体系，发现MgTi_<0.5>Zr_<3.5>（PO_4）_6具有最大的电导率。本文报道了用MgTi_<0.5>Zr_<3.5>（PO_4）_6和Na_2CO_3构成的CO_2气敏元件。以卤化锌、碳酸乙烯酯、碳酸丙二酯、光聚合单体和引发剂为原料，通过光交联和增强制备了多价阳离子导电聚合物固体电解质。这些卤化镁溶液由于其溶解性差而不能制备。室温下ZnBr_2和ZnI_2聚合物电解质的电导率与锂盐的电导率在10^<-5>S·cm ~<-1>（-1）数量级。本文还研究了Zn（CF_3SO_3）_2体系。

There have been many works on inorganic solid electrolytes. Recently, many investigations on polymer solid electrolytes have been done, because of their flexibility and capability of fabrication of thin and light devices. However, studies on multivalent cationic conductive solid electrolytes are few. In this study, multivalent cation, such as Zn or Mg, conductive solid electrolytes both of inorganic and organic types have been investigated. At first, electrical conduction mechanism in solid electrolytes, M^IZr_2 (PO_4) _3, M^<II>Zr_4 (PO_4) _6, and M^<III>Zr_6 (PO_4) _9, with zirconium phosphate framework has been investigated by using frequency dispersion analysis. All solid-state carbon dioxide (CO_2) gas sensor has been constructed by using MgZr_4 (PO_4) _6 [MgZP] and Na_2CO_3 and studied its response characteristics. Improved CO_2 sensor using partially substituted MgZP with Si for PO_4 has been constructed and proved to show higher performance than above mentioned one. A system of partially substituted MgZP with Ti for Zr has been studied by electrical conductivity measurement and XRD analysis to show that MgTi_<0.5>Zr_<3.5> (PO_4) _6 has a maximum electrical conductivity. CO_2 gas sensor constructed by using MgTi_<0.5>Zr_<3.5> (PO_4) _6 and Na_2CO_3 has been reported. Multivalent cation conductive solid polymer electrolytes have been prepared by photo-crosslinking and reinforcing to a micro-porous membrane from precursor solutions of zinc halides, ethylene carbonate, prophlene carbonate, photo-polymerizing monomers, and initiator. Those solutions of magnesium halides could not be prepared because of their poor solubility. The electrical conductivities of the polymer electrolytes of ZnBr_2 and ZnI_2 were in the same order of magnitude of 10^<-5> S cm^<-1> as those of Li salts at room temperature. The system of Zn (CF_3SO_3) _2 has also been investigated.