Development of New Superionic Concucting Glasses and Their Conduction Mechanism

具有与电解质溶液一样高的离子电导率的“超离子导电玻璃”作为固体电解质在发展全固态电池和全固态电致变色显示器中引起了广泛的关注。本研究的目的是开发新的超离子导电玻璃，分析其结构并讨论其导电过程。主要研究结果如下：1.制备了<Ag_2>AgI-Ch-<P_2><Ch_5>（Ch=O，S，Se）体系的导电玻璃，详细研究了O，S，Se含量的变化对玻璃形成能力、玻璃化转变温度、离子电导率、电子电导率、离子迁移数等的影响.制备了<Ag_2>AgX-O-Ge<O_2>（X=I，Br，Cl）体系的离子导电玻璃，并与上述第1项作了对比，研究了I，Br，Cl的钒化对玻璃形成能力，玻璃化温度，结构的影响 ...更多信息 ，等等。3.制备了LiB-LiB系统硫氧化物玻璃<O_2><S_2>作为新型的&lt;Li^+&gt;离子导体.电导率的最大值出现在组分依赖性中，并与“混合碱效应”相对应，命名为“混合阴离子效应”.在Si - B系统中，快速淬火在宽的组成范围内产生玻璃<Li_4><O_4><Li_3>，<O_3>并且还发现电导率的组成依赖性的最大值，类似于Li B-5系统的情况<O_2><LiBS_2>。采用<Li_4><O_4><Li_3><BO_3>射频溅射法和射频磁控溅射法在Si -体系中制备了非晶薄膜，确定了制备非晶薄膜的最佳工艺条件，如靶材成分、气体成分、气压等.用<Li_4><O_4><Li_3><O_3>拉曼散射光谱研究了Si - B玻璃的结构，表明玻璃中只有&lt;Li^+&gt;、&lt;SiO_4^（4-）&gt;和&lt;BO_3^（3-）&gt;。少

The "superionic conducting glasses", which have ionic conductivities as high as those of electrolyte solutions, attract much attension as solid electrolytes in developing all solid state cells and all solid electrochromic displays. The objectives of the present investigation are to develop new superionic conducting glasses, to analyse their structure, and to discuss their conduction processes. The main results obtained are as follows:1. Superionc conducting glasses in the systems AgI- <Ag_2> Ch- <P_2> <Ch_5> (Ch=O,S,Se) were prepared; the influence of variation of O, S and Se was studied in detail on the glass-forming ability, glass transition temperature, ionic conductivity, electronic conductivity, ionic transport number, and so on.2. Superionic conducting glasses in the systems AgX- <Ag_2> O-Ge <O_2> (X=I,Br,Cl) were prepared; in contrast to the above item 1 the influence of vanication of I, Br and Cl was studied on the glass- forming ability, glass transition temperature, structure … More , and so on.3. Oxysulfide glasses in the system LiB <O_2> -LiB <S_2> were prepared as new <Li^+> ion conductors. The maximum of conductivity was found in the composition dependence and named the "mixed anion effect" in contrast to the "mixed alkali effect".4. The rapid quenching produced the glasses in the wide range of composition in the system <Li_4> Si <O_4> - <Li_3> B <O_3> , and the maximum in composition dependence of conductivities was also found, similar to the case of the system LiB <O_2> - <LiBS_2> .5. Amorphous films were prepared in the system <Li_4> Si <O_4> - <Li_3> <BO_3> by the rf sputtering and the rf magnetron sputtering; the optimum conditions were determined for the preparation of the films, such as the target composition, the gas composition, the gas pressure, and so on.6. The structure of the <Li_4> Si <O_4> - <Li_3> B <O_3> glasses was studied by the Raman scattering spectra, indicating that the glasses were composed of only <Li^+> , <SiO_4^(4-)> and <BO_3^(3-)> . Less