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

本文介绍了新研制的含四（烷氧基）铝酸锂络合单元的“铝酸盐”型和含四（烷硫基）铝酸锂络合单元的“硫代铝酸盐”型固体聚电解质。这些固体聚电解质的单离子电导率与混合聚电解质的双离子性质相反，分别高达10 μ S/cm<-6>和10 μ <-5>S/cm。这两种聚电解质在250 ℃以下都是热稳定的，而且无毒，易于一次性使用，在金属锂负极的二次电池中，以TiS_2或氧化态聚苯胺为正极的效果最好。特别是当锂盐的加入量达到理想的双离子导电状态（t +=t-=0.5）时，电池的容量可达20 mAh/g左右，且放电平台电位没有明显衰减。虽然铝酸盐聚合物络合物聚电解质在与金属氧化物阴极材料接触时是稳定的，但相应的硫代铝酸盐类型由于污染的水分而分解。在寻找不燃、安全的电极材料的过程中，我们发现了具有强受主性质的非正常dda石墨（AG）微粉，它将代替一般的钙属化合物。这种AG材料可以打开制备高性能全碳电池如[石墨-Li（阳极）/电解质/AG]的可能性。同时，由于AG可以与高导电性但不稳定的硫代铝酸盐聚电解质组合用作阴极材料，因此它可以提供具有更高容量和电流密度的可再充电电池。

"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.