CN108048870A - 一种嵌入钌硅复合氧化物的镍基活性电极材料及其制备方法 - Google Patents
一种嵌入钌硅复合氧化物的镍基活性电极材料及其制备方法 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003780 insertion Methods 0.000 claims abstract description 5
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- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- 238000006703 hydration reaction Methods 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical class [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
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- 239000010405 anode material Substances 0.000 description 4
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- TTXWERZRUCSUED-UHFFFAOYSA-N [Ru].[Sn] Chemical compound [Ru].[Sn] TTXWERZRUCSUED-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical class OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
本发明提供了一种嵌入钌硅复合氧化物的镍基活性电极材料及其制备方法。所述的活性材料的嵌入体为钌硅复合氧化物，平均颗粒尺度为12 nm，其中Si∶Si+Ru摩尔比为0.18～0.22∶1。所述的嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，采用复合电镀方法，将镍和钌硅复合氧化物同时沉积，获得嵌入钌硅复合氧化物的镍基活性电极材料。该材料具有优越的析氢活性，制备方法简单，可操作性强，原料易得，成本低。
Description
技术领域
本发明属于应用电化学和能源工业的电极材料领域，具体涉及一种具有高催化性能的电极材料及其制备方法。
背景技术
1967年含有贵金属氧化物的电极问世后，人们发现这类氧化物具有非常高的电催化活性，因此被称为活性氧化物材料，或简单称为活性材料。最为优越的活性材料是含钌氧化物，大量研究发现，通过掺杂非贵金属元素不仅可以提高含钌阳极材料的综合性能，而且可以明显降低含钌阳极的制作成本，从而使含钌复合氧化物在许多电化学工业中被大量应用。活性阳极的应用，大幅度提高了电极材料的析氯和析氧活性，降低了电耗。相对于阳极材料，对阴极材料的研究较为薄弱，在许多场合仍然采用电催化活性和稳定性较低的镍金属或钛金属作为阴极材料，严重制约了相关电化学工业领域（包括氯碱工业、氯酸盐工业、制药工业和新能源工业等）的发展。20年前，国外专家发现在镍金属中添加活性更高的组元，形成混合物可以使阴极材料的活性显著提高（Ni+RuO2 co-deposited electrodes forhydrogen evolution，《Electrochemical Acta》2000年45卷4195至4202页）。以后在电化学工业中开发成功了镍基二氧化钌（Ni+RuO2）的活性阴极材料，即在镍金属中嵌入了单元氧化物RuO2。然而到目前为止，人们在如何设计具有嵌入结构的阴极材料，以及如何引入掺杂元素，来提高嵌入体的催化活性和耐蚀性，均未出现新的突破，这与阳极材料的不断进步形成反差。为此，本科研团队主持国家自然科学基金项目，一方面针对可以制作嵌入体的含RuO2复合氧化物的阴极行为进行了系列研究（Ru-Mn氧化物涂层钛阴极的制备与析氢性能，《金属热处理》2009年34卷11期36至39页），另一方面针对具有嵌入结构的阳极材料的相关机理进行了深入研究（Adding a Spinodal Decomposition Retarder: An Approach toImproving Electrochemical Properties of Ruthenium–Tin Complex Oxides，《Journalof Electrochemical Society》2014年161卷10期E119至E127页）。通过系统的分析研究发现，仅有少数几种掺杂RuO2适合用作阴极材料的活性嵌入体。其中，添加一定含量的硅元素的混合氧化物（Ru1-xSixO2）可以制备阴极活性嵌入体，从而开发出可适应于酸性介质的新型镍基复合氧化物（Ni+Ru1-xSixO2）活性阴极材料。
发明内容
本发明的目的在于提供一种嵌入钌硅复合氧化物的镍基活性电极材料及其制备方法。
本发明所述的电极材料中的嵌入体为钌硅复合氧化物，可以采用常规的热分解或共沉积方法制备，平均颗粒尺度为12 nm。
本发明所述的钌硅复合氧化物，其中Si∶Si+Ru摩尔比为0.18～0.22∶1。
本发明所述的在镍基中嵌入钌硅复合氧化物，可以使传统镍基阴极材料的活性得到大幅度的提高，也具有比镍基二氧化钌材料更优越的综合性能，由于采用硅来部分代替贵金属元素钌，使得制作成本显著降低。
本发明所述的镍基钌硅复合氧化物材料，可以应用于氯碱、氯酸盐、水电解、有机溶液电解、超电容、储氢电池、燃料电池等电化学工业中制作阴极部件，其中特别适应于酸性介质的析氢反应。
本发明所述的嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，采用瓦特型电镀方法，在经刻蚀处理的纯镍基材上，将镍和钌硅复合氧化物同时沉积，获得嵌入钌硅复合氧化物的镍基活性电极材料。
本发明的显著优点：
a)本发明在镍基中引入钌硅复合氧化物嵌入体，平均尺度为12 nm左右，使之具有电催化较为合适的纳米嵌入结构，最终获得高度分散的组织结构和高度均匀分布的活性中心，电极材料的活性可以得到大幅度的提高。
b)本发明在钌硅复合氧化物嵌入体中引入适当比例的二氧化硅，其中Si∶Si+Ru摩尔比为0.18～0.22∶1，可以有效利用二氧化硅的高耐蚀性，从而获得的电极材料适宜在酸性介质中析氢的稳定性。
c)本发明选择的制备原料简单，易得，工艺稳定。特别是以高比例的贱金属元素硅替代贵金属元素钌，从而大幅度降低材料成本，达到了实用化和工业化的条件。
具体实施方式
本发明所述的嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，采用复合电镀方法，获得具有嵌入结构的镍基钌硅复合氧化物活性电极材料。
本发明所述的嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，步骤如下：
1）镍基材处理：采用工业纯镍，镍网或镍板材。经去脂，在6 M的硫酸水溶液中刻蚀1小时，去离子水冲洗，干燥。
2）电镀液的配制：电镀液中含有 1.2 M 六水合硫酸镍，0.18 M六水合氯化镍，0.42 M 硼酸，再投加30 g·L-1 钌硅复合氧化物，其中Si∶Si+Ru摩尔比为0.18～0.22∶1。
3) 电镀：将步骤（1）得到的镍基材浸入电镀液中，对电镀液采用机械搅拌，镀液pH值控制在4.4～4.6，镀槽温度50 ℃，电流密度40 mA·cm-2，电量110 C·cm-2，即制成嵌入钌硅复合氧化物的镍基活性电极材料。
以下详细叙述本发明的两个实施例子，但是本发明不仅限制于此。
实施例1
采用工业纯镍N6网材。采用10wt%的洗涤剂去脂，在50℃的6 M的硫酸水溶液中刻蚀1小时，去离子水冲洗，干燥。在含有1.2 M 六水合硫酸镍、0.18 M六水合氯化镍和 0.42 M 硼酸的溶液中，投加经热分解方法制备的平均尺度为12 nm的浓度为30 g·L-1钌硅复合氧化物，其中Si∶Si+Ru摩尔比为0.18∶1。将电镀液加热到 50 ℃，用5M HCl调节镀液pH值为4.5，在机械搅拌下进行电流密度为40 mA·cm-2的恒电流电沉积，电量110 C·cm-2，即制成嵌入钌硅复合氧化物的镍基活性电极材料。采用电化学工作站，采用三电极体系，饱和甘汞电极(SCE)为参比电极, 电解液为0.5 M H2SO4 溶液, 25 ℃测试。测定电极材料析氢的塔菲尔斜率为55 mV·decade-1。具有显著的电催化活性。
实施例2
采用工业纯镍N6网材。采用10wt%的洗涤剂去脂，在50℃的6 M的硫酸水溶液中刻蚀1小时，去离子水冲洗，干燥。在含有1.2 M 六水合硫酸镍、0.18 M六水合氯化镍和 0.42 M 硼酸的溶液中，投加经热分解方法制备的平均尺度为12 nm的浓度为30 g·L-1钌硅复合氧化物，其中Si∶Si+Ru摩尔比为0.22∶1，将电镀液加热到 48 ℃，用5M HCl调节镀液pH值为4.6，在机械搅拌下进行电流密度为40 mA·cm-2的恒电流电沉积，电量110 C·cm-2，即制成嵌入钌硅复合氧化物的镍基活性电极材料。采用电化学工作站，采用三电极体系，饱和甘汞电极(SCE)为参比电极, 电解液为0.5 M H2SO4 溶液，25 ℃测试。测定电极材料析氢的塔菲尔斜率为54 mV·decade-1。具有显著的电催化活性。
实施例3
1）采用工业纯镍N6网材为镍基材。，采用10%的洗涤剂去脂，然后在50℃的、6 mol/LM的硫酸水溶液中刻蚀1小时，去离子水冲洗，干燥；
2）在含有1.2 mol/LM 六水合硫酸镍、0.18 mol/LM六水合氯化镍和 0.42 mol/L M 硼酸的溶液中，投加经热分解方法制备的平均尺度为12 nm的浓度为30 g·/L二氧化钌，制得镀液-1；
3）将电镀液加热到48℃，用5 mol/L HCl调节镀液的pH值为4.6，在机械搅拌下进行电流密度为40 mA·cm-2的恒电流电沉积，电量为110 C·cm-2，即制成嵌入不含硅的二氧化钌的镍基活性电极材料。
采用电化学工作站，采用三电极体系，以饱和甘汞电极(SCE)为参比电极, 电解液为0.5 M H2SO4溶液，25 ℃测试。测得该定电极材料析氢的塔菲尔斜率为93 mV·decade-1。。对比说明，本发明提出的新型电极材料具有显著的电催化活性。
Claims (3)
1.一种嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，其特征在于：具体制备步骤如下：
1）镍基材处理：采用工业纯镍，镍网或镍板材；经洗涤去脂，在6 M的硫酸水溶液中刻蚀1小时，去离子水冲洗，干燥；
2）电镀液配制： 在含有1.2 M 六水合硫酸镍，0.18 M六水合氯化镍，0.45 M 硼酸的电镀液中加入30 g·L-1 钌硅复合氧化物，其中Si∶Si+Ru摩尔比为0.18～0.22∶1；
3) 电镀：将步骤（1）得到的镍基材浸入电镀液中，对电镀液采用机械搅拌，镀液pH值控制在4.4～4.6，镀槽温度50 ℃，电流密度40 mA·cm-2，电量110 C·cm-2，制成嵌入钌硅复合氧化物的镍基活性电极材料。
2.根据权利要求1所述的嵌入钌硅复合氧化物的镍基活性电极材料的制备方法，其特征在于：Si∶Si+Ru摩尔比为0.18～0.22∶1。
3.一种如权利要求1所述方法制备得到的嵌入钌硅复合氧化物的镍基活性电极材料，其特征在于：嵌入钌硅复合氧化物的平均粒径为12 nm。
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