研究Li/SOCl2电池和BCX电池贮存过程正极和负极的交流阻抗谱变化.结果表明,两种电池正、负电极的阻抗都随贮存时间的延长呈先增加而后大致稳定趋势,但如于电解液中添加BrCl,则可使该电极阻抗大大降低,Li电极的阻抗值比添加前降低了近一半,而玻碳电极的则从添加前的~100 kΩ降低到添加后的2kΩ左右;玻碳电极的阻抗值远大于Li电极,是电池的控制电极.
The electrodes in both Li/SOCl2 cells and BCX cells were studied by ac impedance spectroscopy.The results indicate that the resistance of the electrode passive layer increased with the storage time,then became stabilized in both kinds of cells.But the electrode resistance decreased a lot after adding BrCl into the cells.The resistance of the Li electrode decreased about a half to that without BrCl,and the value of the glassy carbon electrode decreased from about 100 kΩ to 2 kΩ.The huge resistance of the glassy carbon electrode indicates that it is the control electrode of the cell.
[1]Boyle G H,Goebel F.Development and characteriza-tion of a high capacity lithium/thionyl chloride battery[J].Journal of Power Sources,1995,54:186-191.
[2]Lafage M,Windel D,Russior V.Mechanisms of growthand corrosion at the lithium-solvent interface[J].Elec-trochimica Acta,1997,42(19):2841-2852.
[3]Liu Jing(刘景),Ge Hong-hua(葛红花),Zhou Guo-ding(周国定),et al.Research status of lithium/thio-nyl chloride battery[J].Battery Bimonthly,2005,35(5):408-410.
[4]Miran Gaberˇscˇek,Stane Pejovnik.Time evolution of theimpedance response of a passive film[J].J Electro-chem Soc,1999,146(3):933-940.
[5]Abraham K M,Alamgir M,Perrotti S T.Some chemis-try in the Li/“SOCl2+BrCl”cell[J].J ElectrochemSoc,1988,135(11):2686-2691.
[6]Liang C C,Krehl P W.Bromine chloride as a cathodecomponent in lithium inorganic cells[J].J Appl Elec-trochem,1981,11:563-571.
[7]Krehl P W,Liang C C.The bromine chloride in the Li/SOCl2battery system[J].J Electrochem Soc,1983,130(13):451-459.
[8]Ge Hong-hua(葛红花),Zhou Guo-ding(周国定),Wu Yi-ping(吴一平),et al.Some characteristics andreaction character of BCX cell[J].Battery Bimonthly,2005,35(6):420-421.
[9]Abraham K M,Mank R M.Some chemistry in the Li/SOCl2cell[J].J Electrochem Soc,1980,127(10):2091-2096.
[10]Walsh F,Pozin M,Cherniy A.Characterization of lith-ium-thionyl chloride cells by impedance techniques[J].Journal of Power Sources,2001,97-98:714-718.
[11]Wu Yi-ping(吴一平),Zhou Guo-ding(周国定),GeHong-hua(葛红花),et al.AC impedance study onLi/SOCl2cell[J].Battery Bimonthly,2006,36(3):175-177.
[12]Zhang Y L,Cha C S.The primary film on the surfaceof a carbon electrode in LiAlCl4-SOCl2electrolyte[J].Electrochimica Acta,1992,37(7):1207-1210.
[13]JakicˇM,Gabersˇcˇek K.Influence of carbon black typeon anode and cathode electrical properties in Li/SOCl2batteries[J].Electrochimica Acta,1995,40(17):2723-2729.
