A novel Co3O4 and WC co-doped β-PbO2 electrode for zinc electrowinning: Deposition behavior and electrochemical properties
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摘要: 采用复合电沉积技术在Pb-0.3wt%Ag/α-PbO2基体上合成了WC和Co3O4颗粒共沉积的β-PbO2复合沉积层。沉积行为研究发现，WC颗粒先于Co3O4颗粒吸附于基体上，将WC颗粒与Co3O4颗粒共沉积是一种抑制当Co3O4颗粒单独共沉积于β-PbO2沉积层时发生团聚情况的有效方法。电极性能研究发现，WC或Co3O4颗粒的共沉积均会提高复合阳极的析氧电催化活性，此外，WC颗粒还有助于提高复合阳极的显微硬度和在Zn电解沉积溶液中的耐腐蚀性能。Co3O4颗粒的共沉积不利于β-PbO2相的生长，WC颗粒的共沉积对β-PbO2相的生长影响不大，两种颗粒同时共沉积有助于抑制酸性镀液中α-PbO2相的生长。Abstract: In this study, the WC and Co3O4 particles co-doped β-PbO2 composite coatings were synthesized on a Pb-0.3wt%Ag/α-PbO2 substrate using composite electrodeposition. The study of deposition behavior has found that WC particles are adsorbed on the substrate before Co3O4 particles, and co-deposition of WC particles and Co3O4 particles is an effective way to inhibit the agglomeration of Co3O4 particles when single co-deposited into β-PbO2 matrix. Electrode performance studies have found that co-deposition of WC or Co3O4 particles can both improve the electrocatalytic activity of oxygen evolution of the composite anode. In addition, WC particles can also help to improve the microhardness of the composite anode and the corrosion resistance in the Zn electrodeposition solution. The co-deposition of Co3O4 particles is not conducive to the growth of the β-PbO2 phase. The co-deposition of WC particles has little effect on the growth of the β-PbO2 phase. The simultaneous co-deposition of two particles helps to inhibit the growth of the α-PbO2 phase in the acid plating solution.
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Key words:
- PbO2 /
- WC /
- Co3O4 /
- Zn electrowinning /
- deposition
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图 3 β-PbO2镀液中不同超声分散时间下的颗粒粒径和Zeta电位
Figure 3. Particle size and Zeta potential for particles in a β-PbO2 plating bath at different ultrasonic dispersion times
图 4 不同沉积时间下的β-PbO2-WC-Co3O4沉积层的XRD图谱
Figure 4. XRD patterns of β-PbO2-WC-Co3O4 coatings obtained at different deposition time
图 5 不同沉积时间下的β-PbO2-Co3O4沉积层的SEM图像和示意图
Figure 5. SEM images and schematic diagram for β-PbO2-Co3O4 coatings obtained at different deposition time
图 6 不同沉积时间下的β-PbO2-WC-Co3O4沉积层的SEM图像和示意图
Figure 6. SEM images and schematic diagram for β-PbO2-WC-Co3O4 coatings obtained at different deposition time
图 7 沉积时间为30 s时获得的β-PbO2-WC-Co3O4沉积层的点扫描能谱
Figure 7. Energy spectrum for the β-PbO2-WC-Co3O4 coating for 30 s of electrodeposition
图 8 沉积时间为2 min时获得的β-PbO2-WC-Co3O4沉积层的点扫描能谱
Figure 8. Energy spectrum for the β-PbO2-WC-Co3O4 coating for 2 min of electrodeposition
图 9 沉积时间为5 min时获得的β-PbO2-WC-Co3O4沉积层的点扫描能谱
Figure 9. Energy spectrum for the β-PbO2-WC-Co3O4 coating for 5 min of electrodeposition
图 10 不同电极在Zn电解沉积模拟溶液中的阳极极化曲线(扫速速率：5 mV/s)
Figure 10. Anodic polarization curves for different electrodes in a simulation Zn electrowinning solution (Scan rate: 5 mV/s)
图 11 不同电极在Zn电解沉积模拟溶液中的Tafel极化曲线(扫速速率：1 mV/s)
Figure 11. Tafel polarization curves for different β-PbO2 coating electrodes in a simulation Zn electrowinning solution (Scan rate: 1 mV/s)
图 12 几种β-PbO2复合沉积层的XRD图谱
Figure 12. XRD patterns for different β-PbO2 coating electrodes
图 13 几种β-PbO2复合沉积层的SEM图像
Figure 13. SEM images for different β-PbO2 coating electrodes
图 14 β-PbO2-WC复合沉积层的线扫描能谱
Figure 14. Energy spectrum for β-PbO2-WC coating by line scanning
图 15 β-PbO2-Co3O4复合沉积层的点扫描能谱
Figure 15. Energy spectrum for β-PbO2-Co3O4 coating by point scanning
图 16 β-PbO2-WC-Co3O4复合沉积层的点扫描能谱
Figure 16. Energy spectrum for β-PbO2-WC-Co3O4 coating by point scanning
图 17 β-PbO2-WC-Co3O4复合电极截面的线扫描能谱
Figure 17. Energy spectrum for the cross section of β-PbO2-WC-Co3O4 coating electrode by line scanning
表 1 不同复合电极的沉积层厚度和表面显微硬度
Table 1. Surface microhardness and resistivity of different composite electrodes
Composite
electrodeCoating
thickness/μmSurface
microhardness (HV)β-PbO2 117.5 738.5 β-PbO2-WC 128.9 821.9 β-PbO2-Co3O4 136.4 679.3 β-PbO2-WC-Co3O4 132.4 762 
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表 2 不同电极在Zn电解沉积模拟溶液中析氧反应(OER)的动力学参数和过电位
Table 2. Kinetic parameters and overpotential for oxygen evolution reaction (OER) of different electrodes in a simulation Zn electrowinning solution
Electrode type Oxygen evolution overpotential η/V a b i0/(A·cm−2) 300 A·m−2 400 A·m−2 500 A·m−2 600 A·m−2 β-PbO2 0.934 0.963 0.986 1.004 1.289 0.233 2.94×10−6 β-PbO2-WC 0.845 0.860 0.871 0.881 1.025 0.118 2.06×10−9 β-PbO2-Co3O4 0.588 0.600 0.609 0.617 0.733 0.095 1.92×10−8 β-PbO2-WC-Co3O4 0.608 0.642 0.668 0.689 1.018 0.269 1.64×10−4 Notes: a—Tafel intercept; b—Tafel slope; i0—Exchange current density.
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表 3 不同电极在Zn电解沉积模拟溶液中的腐蚀电位和腐蚀电流密度
Table 3. Corrosion potentials and corrosion current densities for different β-PbO2 coating electrodes in a simulation Zn electrowinning solution
Electrode type Ecorr(vs SCE)/V icorr/(10−5A·cm−2) β-PbO2 1.312 19.8 β-PbO2-WC 1.314 5.68 β-PbO2-Co3O4 1.298 8.02 β-PbO2-WC-Co3O4 1.37 9.84 Notes: Ecorr—Corrosion potential; icorr—Corrosion current.
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