2,2'-双氨基苯氧基二硫化物及其聚合物的合成研究

在不同的锂或锂离子二次电池正极材料中 ,新型的聚有机二硫化物有可能成为最有应用前景的电池正极材料之一 1] ,Visco等 2 ]首次提出利用二硫化物中双硫键的断裂与再接 (即电聚合与电解聚 )化学性能应用于锂二次电池的充放电 .目前 ,对有代表性的有机二硫化物 2 ,5 -二巯基 -1 ,3 ,4-噻二唑(DMc T)进行了大量的研究3～ 5] ,最近又提出通过合成新的聚有机二硫化物来提高其电化学性能6 ,7] .为了得到一种新型高电化学活性和高导电性的锂或锂离子二次电池正极材料 ,本文通过化学方法合成2 ,2 -双氨基苯氧基二硫化物 (DAPD)单体 ,并通…

Synthesis of 2,2'-Diaminophenyloxydisulfide and Its Polymer

A novel organic disulfide, 2,2'-diaminophenyloxydisulfide(DAPD) has been prepared by the reaction of o-aminophenol with sulfur monochloride in THF. Its polymer films are formed by electropolymerization from a AN/THF solution containing 0.1 mol/L LiClO4, 0.1 mol/L HCl and 0.05 mol/L DAPD monomer on Pt electrode under continuous cycling between -0.30 V and 1.20 V vs. Ag/AgCl (sat. KCl) at scanning rate 50 mV/s. The cyclic voltammetry shows that its electrochemical behavior is similar to that of polyaniline. The redox peak current of the cyclic voltammograms increase with increasing of the cyclic times. The electronic conductivity of poly (DAPD) can reach from 2.1×10-3 to 8.7×10-3 S/cm. Two main facts are considered to be necessary for obtaining electroactive poly (DAPD) in electropolymerization process. One is the existence of sufficient concentration of the supporting electrolyte to enhance the ionic conductivity of AN/THF solution and the other is the existence of protons from the acid HCl. With an increase in acid content of the solution, the polymerization efficiency as well as the electroactivity of poly (DAPD) films show a striking enhancement and the electronic conductivity of poly (DAPD) film increases. But the concentration of HCl would be quite high to result in the decomposition of DAPD monomer.