钽基二氧化钌阴极薄膜电沉积工艺及机理研究
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摘要
电化学超级电容器作为新一代储能元器件具有广泛的应用。钽基二氧化钌阴极薄膜作为超级电容器的关键材料其特点是：该电极材料既保持了充放电效率高、能量密度大，同时具有制备工艺简单、生产效率高等优点，其经济效益和社会效益显著。本论文采用阴极电沉积制备的RuO_2·nH_2O薄膜阴极材料具有适合电化学超级电容器用途的特殊结构和形貌，通过SEM、XRD、Zeta电位、万能电子拉伸试样机和循环伏安等测试手段分析表明：
1、以RuCl_3·xH_2O为电沉积液，KCl、NaNO_3为支持电解质，CTAB为表面活性剂，电沉积制备出了薄膜厚度约4.5μm的RuO_2·nH_2O薄膜。较为详细地研究了该氧化物的制备、形成机理及后续热处理工艺。
2、对电沉积液的浓度、初始pH值、电流密度、电沉积时间和电沉积液温度等工艺参数进行了研究及优化，结果表明：随着电沉积液浓度的增大，薄膜附着力会逐渐变差，通过试验得出RuCl_3·xH_2O电沉积液的浓度5mmol·L~(-1)为最佳浓度值；随着电沉积液初始pH值的升高，RuO_2·nH_2O薄膜越疏松，龟裂纹越大，与基体结合力越差，电沉积液的初始pH值2.1为最佳值；随着电流密度的增大，电沉积后的RuO_2·nH_2O薄膜颜色由基体色逐渐变成深黑色，附着力也随之变差，三段式电沉积最佳电流密度为15mA·cm~(-2)(0—30min)、25mA·cm~(-2)(30—120min)、35mA·cm~(-2)(120—180min)；随着电沉积时间的延长，RuO_2·nH_2O薄膜增厚，但是RuO_2·nH_2O薄膜的开裂倾向增大，电沉积3h可获得较好质量的薄膜；通过对RuO_2·nH_2O薄膜电沉积液温度的实验得知，电沉积温度25℃时较为适宜。
3、采用KCl作为电沉积液的支持电解质制备的RuO_2·nH_2O薄膜龟裂纹粗大，薄膜开裂翘起明显，附着力差；而采用NaNO_3作为电沉积液的支持电解质，得到的RuO_2·nH_2O薄膜龟裂纹细小，薄膜开裂但不翘起，附着力可达12.79MPa。还进一步研究了RuCl_3·xH_2O溶液的性质，RuCl_3.αH_2O(?)RuCl_3.cH_2ORuCl3·xH_2O水解呈胶体形成的胶团带负电荷。添加了CTAB的薄膜整个表面能均匀的覆盖RuO_2·nH_2O，作为阳离子表面活性剂的CTAB对胶体进行了改性，使其在电场作用下易于向阴极定向移动，使胶体粒子易于在阴极上沉积转化，提高了沉积速率并改善了薄膜的质量。
4、稳定化热处理可以提高RuO_2·nH_2O电容的稳定性，但随着薄膜退火温度升高，比电容变化的总体趋势是先升后降，在约100℃时比电容达到最大值，通过电沉积制备的未经稳定化处理的RuO_2·nH_2O薄膜比电容为0.1604F·cm~(-2)，经稳定化退火处理后的薄膜的比电容为1.1325 F·cm~(-2)。
Electrochemical capacitors are playing great roles in widespread application as a new energy store device. For the first time, the systematic exploration was carried out to preparation and characterization and electrochemical capacitance of the hydrous ruthenium oxide film electrode materials with the virtues of simple operating,high efficency, big energy density and charge/discharge efficency. Therefore great social benefits economic benefits could be brought by it. SEM、XRD、Zeta potential and electronic universal testing machine showed that hydrous ruthenium oxide film electrode material developed in our lab exhibits special physical structure and morphology. The main results are as follows:
1.The author researched the preparation and theory of 4.5μm RuO_2·nH_2O films and successional heatreatment etal.RuCl_3·xH_2O, KCl, NaNO_3 and CTAB respectively as the electrodeposition solution, support electrolyte and surface active agent.
2.Concentration of electrolyte, initial pH, current density, time and temperature of electrolyte are optimized by experiment.The results indicate that with the grow of the current density, the adhesion of films will be worse. 5mmol.L~(-1) is a optimum of concentration of electrolyte.With increasing initial pH of RuCl_3·xH_2O solution,loosen film and bad adhesion, the crack will be extended. PH 2.1 is a optimum initial pH. 15mA.cm~(-2) (0 to 30min), 25mA.cm~(-2) (30 to 120min) and 35mA.cm~(-2) (120 to 180min) is a optimum current density. Three hours is a optimum time of electrodeposition; 25℃is a optimum temperature of electrolyte.
3.The crack of RuO_2·nH_2O film is very great with KCl as a supporting electrolyte, the adhesion of film is bad. NaNO_3 is applied to electrodeopsition of RuO_2·nH_2O film as a supporting electrolyte for the first time, the crack of film is very small, the adhesion of film is good and the value is 12.79MPa. Colloid property of RuCl_3·xH_2O solution is studied, RuCl_3.αH_2O(?)RuCl_3.cH_2O that colloid of of RuCl_3·xH_2O solution is electronegative is manifested for the first time; colloid property can be changed with CTAB, so that colloid particle can easily move to cathodic electrode.
4.Heat-treatment can improve the capacitance stability of RuO_2·nH_2O film, but specific capacitance of RuO_2·nH_2O film increase and then decrease with the ascent of temperature. Maximum of specific capacitance occur when the temperature of heat-treatment is about 100℃. The specific capacitance of unannealed RuO_2·nH_2O film is 0.1604F·cm~(-2), the specific capacitance is unsteady; the specific capacitance of annealed RuO_2·nH_2O film is 1.1325F·cm~(-2),the specific capacitance is steady.
1、以RuCl_3·xH_2O为电沉积液，KCl、NaNO_3为支持电解质，CTAB为表面活性剂，电沉积制备出了薄膜厚度约4.5μm的RuO_2·nH_2O薄膜。较为详细地研究了该氧化物的制备、形成机理及后续热处理工艺。
2、对电沉积液的浓度、初始pH值、电流密度、电沉积时间和电沉积液温度等工艺参数进行了研究及优化，结果表明：随着电沉积液浓度的增大，薄膜附着力会逐渐变差，通过试验得出RuCl_3·xH_2O电沉积液的浓度5mmol·L~(-1)为最佳浓度值；随着电沉积液初始pH值的升高，RuO_2·nH_2O薄膜越疏松，龟裂纹越大，与基体结合力越差，电沉积液的初始pH值2.1为最佳值；随着电流密度的增大，电沉积后的RuO_2·nH_2O薄膜颜色由基体色逐渐变成深黑色，附着力也随之变差，三段式电沉积最佳电流密度为15mA·cm~(-2)(0—30min)、25mA·cm~(-2)(30—120min)、35mA·cm~(-2)(120—180min)；随着电沉积时间的延长，RuO_2·nH_2O薄膜增厚，但是RuO_2·nH_2O薄膜的开裂倾向增大，电沉积3h可获得较好质量的薄膜；通过对RuO_2·nH_2O薄膜电沉积液温度的实验得知，电沉积温度25℃时较为适宜。
3、采用KCl作为电沉积液的支持电解质制备的RuO_2·nH_2O薄膜龟裂纹粗大，薄膜开裂翘起明显，附着力差；而采用NaNO_3作为电沉积液的支持电解质，得到的RuO_2·nH_2O薄膜龟裂纹细小，薄膜开裂但不翘起，附着力可达12.79MPa。还进一步研究了RuCl_3·xH_2O溶液的性质，RuCl_3.αH_2O(?)RuCl_3.cH_2ORuCl3·xH_2O水解呈胶体形成的胶团带负电荷。添加了CTAB的薄膜整个表面能均匀的覆盖RuO_2·nH_2O，作为阳离子表面活性剂的CTAB对胶体进行了改性，使其在电场作用下易于向阴极定向移动，使胶体粒子易于在阴极上沉积转化，提高了沉积速率并改善了薄膜的质量。
4、稳定化热处理可以提高RuO_2·nH_2O电容的稳定性，但随着薄膜退火温度升高，比电容变化的总体趋势是先升后降，在约100℃时比电容达到最大值，通过电沉积制备的未经稳定化处理的RuO_2·nH_2O薄膜比电容为0.1604F·cm~(-2)，经稳定化退火处理后的薄膜的比电容为1.1325 F·cm~(-2)。
Electrochemical capacitors are playing great roles in widespread application as a new energy store device. For the first time, the systematic exploration was carried out to preparation and characterization and electrochemical capacitance of the hydrous ruthenium oxide film electrode materials with the virtues of simple operating,high efficency, big energy density and charge/discharge efficency. Therefore great social benefits economic benefits could be brought by it. SEM、XRD、Zeta potential and electronic universal testing machine showed that hydrous ruthenium oxide film electrode material developed in our lab exhibits special physical structure and morphology. The main results are as follows:
1.The author researched the preparation and theory of 4.5μm RuO_2·nH_2O films and successional heatreatment etal.RuCl_3·xH_2O, KCl, NaNO_3 and CTAB respectively as the electrodeposition solution, support electrolyte and surface active agent.
2.Concentration of electrolyte, initial pH, current density, time and temperature of electrolyte are optimized by experiment.The results indicate that with the grow of the current density, the adhesion of films will be worse. 5mmol.L~(-1) is a optimum of concentration of electrolyte.With increasing initial pH of RuCl_3·xH_2O solution,loosen film and bad adhesion, the crack will be extended. PH 2.1 is a optimum initial pH. 15mA.cm~(-2) (0 to 30min), 25mA.cm~(-2) (30 to 120min) and 35mA.cm~(-2) (120 to 180min) is a optimum current density. Three hours is a optimum time of electrodeposition; 25℃is a optimum temperature of electrolyte.
3.The crack of RuO_2·nH_2O film is very great with KCl as a supporting electrolyte, the adhesion of film is bad. NaNO_3 is applied to electrodeopsition of RuO_2·nH_2O film as a supporting electrolyte for the first time, the crack of film is very small, the adhesion of film is good and the value is 12.79MPa. Colloid property of RuCl_3·xH_2O solution is studied, RuCl_3.αH_2O(?)RuCl_3.cH_2O that colloid of of RuCl_3·xH_2O solution is electronegative is manifested for the first time; colloid property can be changed with CTAB, so that colloid particle can easily move to cathodic electrode.
4.Heat-treatment can improve the capacitance stability of RuO_2·nH_2O film, but specific capacitance of RuO_2·nH_2O film increase and then decrease with the ascent of temperature. Maximum of specific capacitance occur when the temperature of heat-treatment is about 100℃. The specific capacitance of unannealed RuO_2·nH_2O film is 0.1604F·cm~(-2), the specific capacitance is unsteady; the specific capacitance of annealed RuO_2·nH_2O film is 1.1325F·cm~(-2),the specific capacitance is steady.
引文
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