锂-氧化铜电池反应机理——Ⅱ.交流阻抗法研究阴极过程

THE REACTION MECHANISM OF Li-CuO CELL Ⅱ.Investigation of the cathode process by a.c.impedance method

本文测量了锂－氧化铜电池和锂－氧化亚铜电池阴极阻抗随电位的变化，与前文［６］中报道的阴极光电流变化作了比较，根据能带理论解释了实验现象。结果表明，锂－氧化铜电池阴极过程中，阴极电位为２．５Ｖ（ｖｓ．Ｌｉ／Ｌｉ＾＋）时，电解液中锂离子开始嵌入氧化铜晶格；当阴极电位降到２．３Ｖ以下时，有后续反应发生，生成氧化亚铜等新相；氧化亚铜的还原开始于１．９Ｖ左右，还确定了锂电池体系中。

The changes of cathode impedances of Li-CuO cell and Li-Cu_2O cell with potential scan were measured,and compared with the changes of the photocurrents of the cathodes reported in the pre- vious article of this series. The results,interpreted on the basis of energy band theory,show that :when Li-CuO cell discharges, Li^+ ions start inserting into CuO lattice at 2.5 V, the succeeding reaction oc- curs below 2.3 V producing Cu_2O,and the reduction of Cu_2O to Cu at 1.9 V. The flatband potentials of Cu_2O and CuO electrodes in 1. 0 mol· L^(-1) LiCIO_4 propylene carbonate solution were also deter- mined.