CN102549197B - 用于电解工艺的阴极 - Google Patents

用于电解工艺的阴极 Download PDF

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CN102549197B
CN102549197B CN201080044876.6A CN201080044876A CN102549197B CN 102549197 B CN102549197 B CN 102549197B CN 201080044876 A CN201080044876 A CN 201080044876A CN 102549197 B CN102549197 B CN 102549197B
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A·L·安托兹
M·布里奇斯
A·卡尔德拉拉
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Abstract

一种用于电解工艺、特别适用于在氯碱电解中析氢的阴极，其由提供有催化涂层的金属基材构成，该催化涂层由两个包含钯、稀土元素(如镨)和选自铂和钌的一种贵金属组分的层组成。外层中稀土元素重量百分比数量比内层中的低。

Description

用于电解工艺的阴极
技术领域
本发明涉及用于电解工艺的电极及其制造方法。
背景技术
本发明涉及用于电解工艺的阴极，特别是适用于在工业电解工艺中析氢的阴极。在下面，将引用氯碱电解作为具有阴极析氢的工业电解的典型工艺，但是本发明不限于特定的应用。在电解工艺工业中，竞争性与几个因素相关，其中主要的是能量消耗的减少，这直接与操作电压相关；这证明了致力于减少后者的各种组分的许多努力，例如欧姆电压降(ohmic drop)，除了阳极和阴极过电压以外，其还取决于工艺参数例如温度、电解质温度和电极间隙。出于该原因，尽管在各种电解工艺中可使用一些失去催化活性的耐化学的金属材料例如碳钢作为析氢阴极，然而，对于减少氢阴极过电压的目的，使用以催化涂层活化的电极变得更为广泛。因而，通过使用例如由提供有氧化钌或铂基催化涂层的镍、铜或钢制成的金属基材，可获得良好的结果。事实上，通过活化阴极的使用可获得的能量节省有时可弥补源自贵重金属基催化剂的使用成本。不管怎样，使用活化阴极的经济便利性基本上取决于它们的操作寿命：为了弥补在氯碱电解槽中安装活化阴极结构的成本，例如必须保证它们的功能持续不短于2或3年的时间周期。然而，大部分的贵金属基催化涂层在偶然的电流反向后遭受巨大的损坏，所述电流反向通常发生于工业工厂的故障情况下：甚至有限的持续时间的阳极电流的通过，导致电势向非常高的值偏移，在一定程度上导致铂或钌氧化物的溶解。在国际专利申请WO2008/043766(以其全文并入本文)中提出了该问题的一个部分解决方案，其公开了在镍基材上获得了提供有由两个相异(distinct)区域构成的涂层的阴极，其中一个区域包含钯和任选的银，具有特别是对于电流反向现象的保护功能，和一个包含铂和/或钌的活化区域，其优选混合有少量的铑，具有用于阴极析氢的催化剂功能。对电流反向现象忍受性(tolerance)的提高主要归因于钯的作用，其可在正常的阴极操作期间形成氢化物；在反向期间，氢化物会被电离来防止电极电势向危险水平偏移。尽管公开于WO2008/043766中的发明证明了在电解工艺中延长活化阴极寿命是有用的，但是仅通过那些包含显著量的铑的配制剂来提供合适的性能；考虑到铑非常高的价格和该金属的有限可获得性，这似乎是使用这种涂层的强烈限制。
因此，显然需要用于工业电解工艺特别是用于具有氢的阴极析出的电解工艺的新型阴极组合物，其特征在于：对于现有技术配制剂而言具有较高的催化活性和在通常使用的操作条件中相等或较高的持续时间和对偶然的电流反向的忍受性。
发明内容
在所附的权利要求中阐述本发明的各个方面。
在一个实施方案中，用于电解工艺的阴极由金属基材构成，例如由镍、铜或碳钢制成，该基材提供有包含至少两个层的催化涂层，所述两个层均包含钯，稀土元素和至少一种选自铂和钌的组分，其中稀土元素的百分比数量在内层中较高(表示为高于45重量％)，并且在外层中较低，表示为10-45重量％。在一个实施方案中，稀土元素的百分比数量在内催化层中为45-55重量％，并且在外催化层中为30-40重量％。在本说明书和本申请的权利要求书中，各种元素的重量百分比数量均是指金属，除非特别说明。所示的元素可以以原样或以氧化物或其它化合物的形式存在，例如铂和钌可以以金属或氧化物的形式存在，稀土金属主要为氧化物，钯在制造电极时主要为氧化物并且在析氢下于操作条件下主要为金属。本发明人意外地观察到：当确定了一定的成分梯度时，特别是当稀土元素含量在最外层中为较低时，催化层内稀土元素的数量更有效地显示了它对于贵金属(noble)成分的保护作用。不希望本发明为任何特定的理论所束缚，可以假设外层中稀土元素减少的数量使得铂或钌催化位点对于电解质更可进入，而不显著改变涂层的总体结构。在一个实施方案中，稀土元素包含镨，尽管本发明人发现同族的其它元素例如铈和镧也能够显示具有类似结果的类似作用。在一个实施方案中，催化涂层不含铑；在最外层中具有减少量的稀土元素的催化涂层配制剂的特征在于：极低的析氢阴极过电压，使得使用铑作为催化剂变为不必要的。考虑到铑的价格一贯保持高于铂和钌的价格的趋势，这可具有在显著程度上减少电极制造成本的优点。在一个实施方案中，以金属计，钯与贵金属组分的重量比为0.5∶2；这可具有提供充足阴极活性以及使催化剂免于偶然电流反向现象的合适保护的优点。在一个实施方案中，在这样的配制剂中钯含量可部分为银所取代，例如具有0.15∶0.25的Ag/Pd摩尔比。这可具有改善在操作期间钯吸收氢和在偶然的电流反向期间氧化所吸收的氢的能力。
在一个实施方案中，通过前体溶液的氧化热解，即通过至少两种顺序施加的溶液的热分解，获得上面描述的电极。两种溶液均包含钯的盐或其它可溶性化合物、稀土元素例如镨的盐或其它可溶性化合物和至少一种贵金属例如铂或钌的盐或其它可溶性化合物，条件是，意在形成最外面的催化层的最后施加的溶液具有的稀土元素百分比数量低于第一施加溶液的稀土元素百分比数量。在一个实施方案中，前体溶液中所包含的盐是硝酸盐，并且在空气存在下在430-500℃的温度下进行它们的热分解。
在以下实施例中给出一些由本发明人获得的最显著的结果，这并不意在作为本发明范围的限制。
实施例1
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(50g/L)和Pd(II)硝酸盐(20g/L)的水溶液的5个涂层镀覆网状物，在每个涂层后在450℃下进行15分钟热处理直至获得1.90g/m2Pt、1.24g/m2Pd和3.17g/m2Pr(内催化层形成物)的沉积。在这样获得的催化层上，施加包含用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(27g/L)和Pd(II)硝酸盐(20g/L)的第二溶液的4个涂层，在每个涂层后在450℃下进行15分钟热处理直至获得1.77g/m2Pt、1.18g/m2Pd和1.59g/m2Pr(外催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-924mV/NHE的欧姆校准(ohmic-corrected)的初始平均阴极电势，对应于优异的催化活性。
随后在10mV/s的扫描速率下，在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为15mV，对应于对电流反向的优异忍受性。
实施例2
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(50g/L)和Pd(II)硝酸盐(20g/L)的水溶液的3个涂层镀覆网状物，在每个涂层后在460℃下进行15分钟热处理直至获得1.14g/m2Pt、0.76g/m2Pd和1.90g/m2Pr(内催化层形成物)的沉积。在这样获得的催化层上，施加包含用硝酸酸化的Pt(II)二氨基二硝酸盐(23.4g/L)、Pr(III)硝酸盐(27g/L)和Pd(II)硝酸盐(20g/L)的第二溶液的6个涂层，在每个涂层后在460℃下进行15分钟热处理直至获得1.74g/m2Pt、1.49g/m2Pd和2.01g/m2Pr(外催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-926mV/NHE的欧姆校准的初始平均阴极电势，对应于优异的催化活性。
随后在10mV/s的扫描速率下在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为28mV，虽然比实施例1的电极低一些，但是对应于对电流反向仍可接受的忍受性；这归因于内催化层中稀土元素的百分比含量(65％)比随后确定为优化值的值(45-55％)略高一些的事实。
实施例3
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Ru(III)亚硝基硝酸盐(30g/L)、Pr(III)硝酸盐(50g/L)、Pd(II)硝酸盐(16g/L)和AgNO3(4g/L)的水溶液的5个涂层镀覆网状物，在每个涂层后在430℃下进行15分钟热处理直至获得1.90g/m2Ru、1.01g/m2Pd、0.25g/m2Ag和3.17g/m2Pr(内催化层形成物)的沉积。在这样获得的催化层上，施加包含用硝酸酸化的Ru(III)亚硝基硝酸盐(30g/L)、Pr(III)硝酸盐(27g/L)、Pd(II)硝酸盐(16g/L)和AgNO3(4g/L)的第二溶液的6个涂层，在每个涂层后在430℃下进行15分钟热处理直至获得2.28g/m2Ru、1.22g/m2Pd、0.30g/m2Ag和2.05g/m2Pr(外催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-925mV/NHE的欧姆校准的初始平均阴极电势，对应于优异的催化活性。
随后在10mV/s的扫描速率下在从1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为12mV，对应于对电流反向的优异忍受性。
实施例4
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、La(III)硝酸盐(50g/L)和Pd(II)硝酸盐(20g/L)的水溶液的5个涂层镀覆网状物，在每个涂层后在450℃下进行15分钟热处理直至获得1.90g/m2Pt、1.24g/m2Pd和3.17g/m2La(内催化层形成物)的沉积。在这样获得的催化层上，施加包含用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、La(III)硝酸盐(32g/L)和Pd(II)硝酸盐(20g/L)的第二溶液的3个涂层，在每个涂层后在450℃下进行15分钟热处理直至获得1.14/m2的Pt、0.76g/m2的Pd和1.22g/m2的La(外催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-928mV/NHE的欧姆校准的初始平均阴极电势，对应于优异的催化活性。
随后在10mV/s的扫描速率下在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为22mV，对应于对电流反向的优异忍受性。
对比实施例1
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(50g/L)、Rh(III)氯化物(4g/L)和Pd(II)硝酸盐(20g/L)的水溶液的7个涂层镀覆网状物，在每个涂层后在450℃下进行15分钟热处理直至获得2.66g/m2Pt、1.77g/m2Pd、0.44g/m2Rh和4.43g/m2Pr(根据WO2008/043766的催化层的形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-930mV/NHE的欧姆校准的初始平均阴极电势，尽管比前面存在铑的实施例低，但这仍对应良好的催化活性。
随后在10mV/s的扫描速率下在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为13mV，对应于对电流反向的优异忍受性。
对比实施例2
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(50g/L)和Pd(II)硝酸盐(20g/L)的水溶液的7个涂层镀覆网状物，在每个涂层后在460℃下进行15分钟热处理直至获得2.80g/m2Pt、1.84g/m2Pd和4.70g/m2Pr(催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-936mV/NHE的欧姆校准的初始平均阴极电势，可能由于催化配制剂中不存在铑所以比对比实施例1的低，这对应平均至良好的催化活性。
随后在10mV/s的扫描速率下在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为80mV，对应于对电流反向差的忍受性。
对比实施例3
使100mm×100mm×0.89mm尺寸的镍200网状物经受用金刚砂的喷砂处理，然后在20％的煮沸的HCl中蚀刻5分钟。随后用硝酸酸化的Pt(II)二氨基二硝酸盐(30g/L)、Pr(III)硝酸盐(28g/L)和Pd(II)硝酸盐(20g/L)的水溶液的6个涂层镀覆网状物，在每个涂层后在480℃下进行15分钟热处理直至获得2.36g/m2Pt、1.57g/m2Pd和2.20g/m2Pr(催化层形成物)的沉积。
使样品经受操作测试，在3kA/m2下，在33％的NaOH中析氢下，在90℃的温度下，显示了-937mV/NHE的欧姆校准的初始平均阴极电势，如在对比实施例2中的那样，这对应平均至良好的催化活性。
随后在10mV/s的扫描速率下在从-1至+0.5V/NHE的范围内使相同的样品经受循环伏安法；在25个循环后平均阴极电势变化为34mV，对应于比对比实施例2中好的对电流反向的忍受性，最可能是由活化中不同的贵金属与稀土元素的比例所致，但是仍然是不令人满意的。
前面的描述不是要限制本发明，可以根据不同的实施方案使用它们而不背离本发明的范围，并且其程度由所附的权利要求明确地限定。
在本申请的说明书和权利要求中，术语“包含”及其变体例如“包括”和“含有”不是要排除其它要素或添加剂的存在。
在本说明书中包含文件、法案、材料、器件和制品等的讨论仅是为了提供本发明的背景。不代表或表示这些事项的任一种或全部形成现有技术基础的一部分或者在本申请的各权利要求的优先权日之前在本发明的相关领域中是公知常识。

Claims (9)

1.用于电解工艺的阴极，其由提供有多层催化涂层的金属基材构成，该多层催化涂层包含至少一个内催化层和一个外催化层，内催化层和外催化层均包含钯、至少一种稀土元素和至少一种选自铂和钌的贵金属组分，其中所述外催化层具有10-45重量％的稀土元素含量，并且所述内催化层具有高于所述外催化层的稀土元素含量。
2.根据权利要求1的阴极，其中所述外催化层具有30-40重量％的稀土元素含量，并且所述内催化层具有45-55重量％的稀土元素含量。
3.根据权利要求1或2的阴极，其中所述至少一种稀土元素为镨。
4.根据权利要求1或2的阴极，其中所述催化涂层不含铑。
5.根据权利要求1或2的阴极，其中所述催化涂层包含银。
6.根据权利要求5的阴极，其中钯和银的总和与所述贵金属组分的重量比为0.5：2，以元素计。
7.用于制造根据权利要求1-4中任一项的阴极的方法，其包括：第一前体溶液的多涂层热分解，该第一前体溶液包含Pd的至少一种盐、Pr的至少一种盐和选自Pt和Ru的贵金属的至少一种盐，接着是第二前体溶液的多涂层热分解，该第二前体溶液包含Pd的至少一种盐、Pr的至少一种盐和选自Pt和Ru的贵金属的至少一种盐，其中相对于金属的总和，所述第二前体溶液具有的Pr的百分比含量低于所述第一前体溶液中Pr的百分比含量。
8.根据权利要求7的方法，其中所述Pd、Pr、Pt和Ru的盐为硝酸盐，并且在430-500℃的温度下进行所述的热分解。
9.用于碱金属氯化物盐水的电解的电解槽，其包含至少一个根据权利要求1-6中任一项的阴极。
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