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，由于聚合物固体电解质具有柔性和制造轻薄器件的能力，人们对其进行了大量的研究。然而，对多价阳离子导电固体电解质的研究却很少。在本研究中，研究了多价阳离子，如Zn或Mg，无机和有机类型的导电固体电解质。首先用频散分析方法研究了固体电解质M^IZr_2 (PO_4) _3、M^<II>Zr_4 (PO_4) _6和M^<III>Zr_6 (PO_4) _9在磷酸锆框架下的导电机理。采用MgZr_4 (PO_4) _6 [MgZP]和Na_2CO_3制备了全固态二氧化碳（CO_2）气体传感器，并对其响应特性进行了研究。用Si代替PO_4部分取代MgZP的改进型CO_2传感器已制成，并证明其性能优于上述传感器。通过电导率测量和XRD分析，研究了Ti部分取代MgZP的体系，结果表明，MgTi_<0.5>Zr_<3.5> (PO_4) _6具有最大的电导率。用MgTi_<0.5>Zr_<3.5> (PO_4) _6和Na_2CO_3构筑了CO_2气体传感器。以卤化锌、碳酸乙烯、碳酸乙烯、光聚合单体和引发剂为前驱体溶液，通过光交联并增强至微孔膜制备了多价阳离子导电固体聚合物电解质。这些卤化镁溶液由于溶解度差而无法制备。ZnBr_2和ZnI_2聚合物电解质在室温下的电导率与Li盐相同，均为10^<-5> S cm^<-1>。对Zn (CF_3SO_3) _2体系进行了研究。

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.