化学学报 ›› 1981, Vol. 39 ›› Issue (3): 193-202.    下一篇

论文

镉-氧化汞电池低温放电电压滞后现象的研究

庄继华, 毛君国, 章惠方, 陈霞玲, 周伟舫   

  1. 复旦大学化学系, 上海
  • 投稿日期:1979-03-08 发布日期:2013-06-03

STUDIES ON THE VOLTAGE DELAY OF CADMIUM-MERCURIC OXIDE CELLS AT LOW TEMPERATURES

ZHUANG JI-HUA, MAO JUN-GUO, ZHANG HUI-FANG, CHEN XIA-LING, ZHOU WEI-FANG   

  1. Department of Chemistry, Fu Dan University, Shanghai
  • Received:1979-03-08 Published:2013-06-03

镉-氧化汞扣式碱性电池在低温(如-40℃)放电时有较严重的电压滞后现象.此种滞后现象是由氧化汞电极所产生的.本工作应用恒电流和动态恒电位等极化方法研究氧化汞电极的电极反应.氧化汞电极的滞后电压随温度升高而减小,随放电率的增高而增大,且能达最大值.此最大滞后电压几与温度无关,但与电极中所含导电材料的性质有关.例如,使用银粉作为导电材料时所测得的最大滞后电压约为40毫伏,而镍粉则约为140毫伏.电池中的电毛细活性杂质会加重电压滞后现象.例如,若在电池中使用化学稳定性较差的隔膜,则其电压滞后现象会因电池搁置时间的增长而更为严重.上述电压滞后现象是由于氧化汞电极在阴极还原时的新相形成超电努所造成的,最大滞后电压即相当于形成最小生长核心时的新相形成超电势.

The voltage delay of the 70 mah cadmium-mercuric oxide button cell was severe at low temperatures, especially when it was kept several hours at -400℃. As proved by previous work, the delay phenomenon is caused by the mercuric oxide electrode, but not the cadmium electrode, Galvanostatic and potentiodynamic techniques were used to investigate the electrode reactions in mercuric oxide cathodes. The delayed voltage of the mercuric oxide cathode increased with decreasing temperature or increasing discharge rate, and roachod a maximum value which was almost independent on temperature, but dependent on the conducting material used in the mercuric oxide electrode (e. g. about 140 mV for Ni and 40 mV for Ag, respectively). Nylon felt containing PVA and CMC was used as diaphragm in the cell. It appreciably increased delayed voltage after the cell had been stored for 1 month. The voltage delay of the cell during constant current discharge is due to the slowness of formation of nuclei on the substrates of the mercuric osido cathode, and the maximum delayed voltage corresponds to the overvoltage of forming smallest nuclei on the cathode.