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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (6): 985-990. 上一篇    下一篇

研究论文

复合氧化物Ca_(1-x)Pb_xMnO_(3-σ)的合成及其电化学性能研究

夏熙;李兴琴   

  1. 新疆大学应用化学所,乌鲁木齐(830046)
  • 发布日期:2002-06-15

Studies on the Synthesis of Ca_(1-x)Pb_xMnO_(3-σ) and Its Electrochemical Performance

Xia Xi;Li Xueqin   

  1. Institute of Applied Chemistry, Xinjiang University,Wulumuqi(830046)
  • Published:2002-06-15

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被引次数

26 | 4

采用共沉淀法制得Ca_(1-x)Pb_xMnO_(3-σ)的XRD测试结果表明该样品具有钙 钛结构，利用X射线光电子能谱(XPS)对Ca_(0.9)Pb_(0.1)MnO_(3-σ)样品中各元素 的价态进行了鉴定，结果表明各元素分别以Ca~(2+)，Pb~(4+)，Mn~(4+)以及少量 的Mn~(3+)的形式存在。四探针电导率测试结果发现Ca_(0.9)Pb_(0.1)MnO_(3-σ) 的电导率比无取代CaMnO_(3-σ)样品的电导率提高了将近两个数量级。并且半导体 的类型发生了变化。在碱性溶液中Ca_(0.9)Pb_(0.1)MnO_(3-σ)表现出良好的电化 学性能，9 mol/L KOH电解质溶液中，50 mg样品采用2 mA放电至-0.8 V时放电容量 为384 mA·h/g左右。并利用循环伏安对其充放电机理进行了初步探讨。

关键词: 钙钛矿型结构, 氧化钙, 氧化锰, 氧化铅, 电导率, 电化学, X射线光电子谱法, 循环伏安法

A series samples of Ca_(1-x)Pb_xMnO_(3-σ) have been synthesized by co-deposition method. Their structures were analyzed and characterized by X-ray diffraction (XRD) and X-ray electron spectroscopy (XPS). The results show that these samples are perovskite-type structure with Ca~ (2+), Pb~(4+), and Mn~(4+) respectively and a minor amount of Mn~(3+). The conductivity value of Ca_(0.9)Pb_(0.1)MnO_(3-σ) is two orders of magnitude higher than that of CaMnO_(3-σ) and the semiconductivity- type changes from n-type for CaMnO_(3-σ) to p-type for Ca_(0.9)Pb_(0.1) MnO_(3-σ). The discharge capacity of Ca_(0.9)Pb_(0.1)MnO_(3-σ) in 9 mol/L KOH solution is about 380 mA·h/g at the discharge regime — 2 mA galvanostatic to cutoff voltage of -0.8 V(vs. Hg/HgO). Cyclic voltammetry and galvanostatic charge-discharge studies show Ca_(0.9) Pb_(0.1)MnO_(3-σ) has a better rechargeability than the International common Sample (I. C. No. 1) in alkaline solution. The mechanism is preliminarily discussed.

Key words: PEROVSKITE TYPE STRUCTURE, CALCIUM OXIDE, MANGANESE OXIDE, LEAD OXIDE, ELECTRICAL CONDUCTIVITY, ELECTROCHEMISTRY, XRD, CYCLOVOLTAMGRAPH

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