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材料研究学报  2017, Vol. 31 Issue (10): 765-772    DOI: 10.11901/1005.3093.2016.581
  研究论文 本期目录 | 过刊浏览 |
离子液体对PbO2电沉积形核生长过程的影响研究
薛娟琴(), 张健, 王磊, 于丽花, 唐长斌, 毕强
西安建筑科技大学冶金工程学院 西安 710055
Influence of Ionic Liquid [Emim]BF4 on Nucleation and Growth of PbO2 during Electrodeposition
Juanqin XUE(), Jian ZHANG, Lei WANG, Lihua YU, Changbin TANG, Qiang BI
School of Metallurgical Engineering, Xi'an University Of Architecture and Technology, Xi'an 710055, China
引用本文:

薛娟琴, 张健, 王磊, 于丽花, 唐长斌, 毕强. 离子液体对PbO2电沉积形核生长过程的影响研究[J]. 材料研究学报, 2017, 31(10): 765-772.
Juanqin XUE, Jian ZHANG, Lei WANG, Lihua YU, Changbin TANG, Qiang BI. Influence of Ionic Liquid [Emim]BF4 on Nucleation and Growth of PbO2 during Electrodeposition[J]. Chinese Journal of Materials Research, 2017, 31(10): 765-772.

全文: PDF(1140 KB)   HTML
摘要: 

为揭示1-乙基-3-甲基-咪唑四氟硼酸盐([Emim]BF4)添加对PbO2阳极形核和生长过程的影响机制,利用电化学工作站测试PbO2在玻碳电极上沉积的电化学行为特征,包括：循环伏安曲线、计时电位曲线及计时电流曲线,并与氧化沉积的PbO2涂层表面形貌进行对比分析。结果表明,PbO2电沉积过程遵循三维连续成核模式,离子液体辅助时虽未明显改变PbO2电结晶机理,但对PbO2电沉积过程中成核和结晶长大速率均有抑制作用,其中以抑制核长大为主,从而明显地减小了PbO2结晶颗粒尺寸,得到致密的电极表面结构,使得电化学综合性能增强。
关键词 ： 金属材料,  PbO2,  电沉积,  形核生长,  离子液体    
Abstract：

The effect of 1- ethyl -3- methyl imidazole tetrafluoroborate ([Emim]BF4) on the nucleation and growth of PbO2 coating on glassy carbon electrode was studied during the electrodeposition process by means of in-situ cyclic voltammetry, chronopotentiometry and chronoamperometry with an electrochemical workstation. Besides, the surface morphology and crystal structure of PbO2 coating was characterized by SEM and XRD. The results show that PbO2 electrodeposition process follows the three-dimensional continuous nucleation model, the addition of ionic liquid in the electrolyte does not significantly change the electrocrystallization mechanism of PbO2, but can inhibit the nucleation and crystal growth rate of PbO2, so as to decrease the PbO2 grain size, densify the coating and enhance the electrochemical performance of the resulted PbO2 electrode.
Key words： metallic materials    PbO2    electrodeposition    nucleation growth    ionic liquid [Emim]BF4
收稿日期: 2016-10-08     
ZTFLH:  TQ153  
基金资助:国家自然科学基金(51478379,51408468),陕西省自然科学基金重大基础研究项目(2017ZDJC-25),陕西省教育厅专项科研计划(16JK1422)
作者简介:

作者简介 薛娟琴,女,1966年生,教授,博士
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薛娟琴
张健
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于丽花
唐长斌
毕强

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https://www.cjmr.org/CN/10.11901/1005.3093.2016.581      或      https://www.cjmr.org/CN/Y2017/V31/I10/765

图1  PbO2在玻碳电极上电沉积过程的循环伏安曲线
图2  PbO2在玻碳电极上电沉积过程的电位-时间暂态曲线
图3  不同过电位下PbO2在玻碳电极上电沉积过程的电流-时间暂态曲线
图4  不同过电位下PbO2在玻碳电极上电沉积的电流-时间暂态无因次曲线与理论成核曲线对比
η /
mV		 tm/s 10-3Im
/mAcm-2		 10-7Im2tm
/A2scm-4		 10-10 K 10-7D
/cm2s-1		 104AN0
/cm-2s-1		 A/s-1 106 Ns/cm-2
10 11.00 401.662 17.75 20.9 2.04 3.26 1.04 2.08
20 7.00 468.754 15.38 24.3 1.77 9.29 1.14 3.77
30 5.25 563.833 16.69 29.3 1.92 15.20 1.68 4.63
40 4.50 605.085 16.50 31.4 1.90 20.90 1.76 5.45
50 3.25 694.720 15.70 36.1 1.81 42.10 2.73 7.93
表1  PbO2在玻碳电极上电沉积暂态电流曲线的动力学参数分析
η /
mV		 tm/s 10-3 Im
/mAcm-2		 10-7Im2tm
/A2scm-4		 10-10K 10-7D
/cm2s-1		 104AN0
/cm-2s-1		 A/s-1 106 Ns/cm-2
20 7.75 482.556 18.05 25.05 2.07 6.48 1.08 2.91
30 6.25 520.817 16.95 27.04 1.95 10.58 1.36 3.83
40 4.00 608.459 14.80 31.60 1.71 29.45 2.03 6.82
50 3.50 647.641 14.70 33.62 1.69 38.92 2.31 7.89
60 2.50 805.364 16.20 41.81 1.87 68.94 3.24 9.96
表2  添加50 mg/L[Emim]BF4后PbO2在玻碳电极上电沉积暂态电流曲线的动力学参数分析
图5  晶体生长速率与过电位关系曲线
图6  形核速率常数与过电位关系曲线
图7  饱和晶核密度与过电位关系曲线
图8  不同镀液条件下制备钛基PbO2的SEM图
图9  不同镀液条件下制备钛基PbO2的截面SEM图
图10  不同镀液制备的PbO2镀层的XRD图谱
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