Studies on the Solid Polyelectrolytes for Rechargeable Film-type Lithium Batteries.

“铝酸盐”型固体聚电解质载四(烷氧基)铝酸锂络合物单元或“硫代铝酸盐”型负载四(烷硫基)铝酸盐络合物单元是最新发展起来的。这些固体聚电解质具有单离子导电性，而杂化聚电解质的双离子导电性分别高达10^lt；-6和10^lt；-5&gt；S/cm。两种聚电解液的热稳定性均高达250ﾟC，且无毒，易于一次性使用。在偏锂正极电池的试验中，以TiS_2或氧化态聚苯胺作正极效果最好。特别是当在聚电解质中加入适量的锂盐以实现理想的双离子导电时，t+=t-=0.5，在放电平台电位没有明显衰减的情况下，获得了约20mAh/g的高容量。当铝酸盐聚合物复合聚电解质与金属氧化物正极材料接触时是稳定的，而相应的硫代铝酸盐类型由于污染水分而分解。硫代铝酸盐的正极材料只有硫化物或硒化合物，在寻找非易燃、安全的电极材料的过程中，我们发现了具有很强受主性质的不规则的DDA石墨(AG)微粉，将取代普通的钙化物。这种AG材料可用于制备高性能的全碳电池，如[石墨-Li(阳极)/电解液/AG]。同时，由于银可以作为正极材料与高导电性但不稳定的硫铝酸盐聚电解液相结合，可以为二次电池提供更高的容量和电流密度。

"Aluminate"solid polyelectrolytes carrying lithium tetra (alkoxy) aluminate complex units or "Thioaluminate"types carrying tetra (alklthio) aluminate complex units were newly developed. These solid polyelectrolytes gave single ionic conductivity on the contrary to the bi-ionic nature of hybrid polyelectrolytes as high as 10^<-6> and 10^<-5>S/cm, respectively. Both polyelectrolytes are thermally stable up to 250ﾟC,and easily disposable becausse of non-toxicity.Among the examination of rechargeable batteries with metakkic lithium anodes, the best results were obtained when TiS_2 or oxidized state polyaniline were used as cathodes. Especially when the extra lithium salts were added to the polyelectrolyte in suitable amount in order to realize the ideal bi-ionic conduction, t_+=t_-=0.5, high capacity of about 20 mAh/g was established without the significant decay of discharging plateau potential. While the aluminate polymer complex polyelectrolytes were stable in contact with metal oxide cathode materials, the corresponding thioaluminate types decomposed due to contaminating moisture. Only sulfide or selenide calcogen materials were available as cathode materials in the case of thioaluminates.During the course to search for non-flameable and safe electrode mataerials, we found anormalous dda graphite (AG) fine powders with strong acceptor properties which will be used in stead of ordinary calcogenides. This AG material may open the possibility to prepare high performance all carbon cells such as [Graphite-Li (anode) /electrolyte/AG]. At the same time, as AG can be used as a cathode material in combination with the highly conductive but unstable thioaluminate polyelectrolytes, it may provide the rechargeable batteries with higher capacity and current density.