The Design And Synthesis Of Subphthalocyanine Complexes And Their Catalytic Performance For Lithium/thionyl Chloride Batteries

Subphthalocyanine(SubPcs)is lower homologues of phthalocyanine.Subphthalocyanines are cone-shaped,aromatic macrocycles made of three diminoisoindoline units N-fused around a boron atom.Their delocalized 14-π-system characteristic confers them interesting aromatic properties,chemical durability,optical properties,nonlinear optical properties.Moreover,these properties may be easily fine-tuned by the modification of their peripheral and axial positions.Li/SOCl2 battery,having high battery voltage and energy density,is a very useful electrochemical power source.Li/SOCl2 battery’s high theoretical open-circuit voltage,operating voltage,high-rate capability,long shelf-life and wide range of operational temperature make it an ideal candidate for instrumentation systems,telecommunication facilities,security systems,search and rescue equipments,medical electronic equipments and monitoring systems.However,due to the voltage delay and security problem,the energy density of the battery in practice is much lower than that in theory.It greatly limits the application of the Li/SOCl2 battery.So,extensive research efforts have been done to improve the practical energy of Li/SOCl2 battery.Subphthalocyanines used as catalyst attracts our attention.The discharge voltage and the discharge time of the batteries catalyzed by the Subphthalocyanine are hoped to increase.4-Nitrophthalonitrile and four kinds of phenol compounds were used to synthesize four different precursors.Then,the precursors react with BBr3 under nitrogen atmosphere,respectively.So,three kinds of mononuclear Subphthalocyanines and one dinuclear Subphthalocyanine were prepared.In addition,Br-BsubPc(NO2)3 was reduced to synthesize Br-BsubPc(NH2)3.At last,seven different phenol compounds were used to modify the axial of all the subphthalocyanines prepared above.And they are all characterized by element analysis,IR,and UV spectra.The discharge property and the cyclic voltammetry measurements were tested in the simulative batteries.It can be found that:(1)The catalytic activity of the compounds having-COOCH3,-COOH and-CHO on the axial is relatively better than the others.(2)The result of the cyclic voltammetry measurements showed that there is a two-step electron transfer in the reaction of Li/SOCl2 battery and the reaction occurred in the discharge process is irreversible.(3)The catalytic activity of subphthalocyanines is related to not only the rings of the compounds,but also the substitution on the axial situation.