CN116334656A - 碱性电解水制氢用的膜电极及其制备方法 - Google Patents
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Abstract
本发明涉及电解水技术领域,具体涉及一种碱性电解水制氢用的膜电极及其制备方法。该膜电极包括多孔隔膜和分别负载于所述多孔隔膜两侧的析氢催化剂和析氧催化剂;所述多孔隔膜选自聚砜、聚醚砜、聚四氟乙烯、聚偏氟乙烯或聚苯硫醚多孔膜中的一种。与传统分离式的隔膜‑Ni网电极组合相比,本发明所述的膜电极采用更薄的高分子多孔隔膜,降低电解水的过电势,同时催化剂与隔膜形成牢固的粘结力,不易脱落,有助于提高膜电极电解水性能的稳定性。
Description
技术领域
本发明涉及电解水技术领域,具体涉及一种碱性电解水制氢用的膜电极及其制备方法。
背景技术
随着全球对环保脱碳的日益关注以及可再生能源发电技术的进步,利用风电、光电和水电等可再生能源制氢是实现绿色氢能经济的重要途径。氢能可广泛应用于甲醇生产、油品加氢、合成氨、金属冶炼、供热及车用运输等。可再生能源总量增速显著,将成为主要能源之一,其发电成本随着技术的成熟和规模的扩大在不断下降,可再生能源制氢有望具备市场竞争力。另外,可再生能源制氢可消纳弃风、弃光和弃水电力,获得低成本氢气。
电解水制氢技术包括碱性电解水制氢、质子交换膜电解水制氢、阴离子交换膜电解水制氢和固体氧化物电解水制氢。其中,碱性电解水制氢技术最为成熟,已广泛应用于火电厂和精密电子产品生产等领域。该技术具有设备成本低、寿命长和稳健的优点,但仍存在电流密度低和电解能耗高的缺点。因此,降低电解水的过电势,提高电解能效和电流密度是解决的关键问题。
发明内容
本发明的目的是为了克服现有技术存在的碱性电解水制氢电流密度低,电解能耗高的缺陷,提供一种电解水制氢用的膜电极,该膜电极能够降低电解水的过电位,提高电解水的能量效率和电流密度。
为了实现上述目的,本发明一方面提供一种碱性电解水制氢用的膜电极,该膜电极包括多孔隔膜和分别负载于所述多孔隔膜两侧的析氢催化剂和析氧催化剂;所述多孔隔膜选自聚砜、聚醚砜、聚四氟乙烯、聚偏氟乙烯或聚苯硫醚多孔膜中的一种。
本发明第二方面提供一种所述膜电极的制备方法,该方法包括:析氢催化剂和析氧催化剂的通过物理气相沉积法分别负载于多孔隔膜两侧。
与传统分离式的隔膜-Ni网电极组合相比,本发明所述的膜电极采用更薄的高分子多孔隔膜,降低电解水的过电势,同时催化剂与隔膜形成牢固的粘结力,不易脱落,有助于提高膜电极电解水性能的稳定性;本发明通过磁控溅射法将析氢和析氧催化剂镀在高分子多孔隔膜两侧,催化剂分散度高,进一步降低电解水的过电位,提高膜电极电解水性能的稳定性。
附图说明
图1是本发明实施例4制备的膜电极的SEM图;
图2是对比例1制备的阴极Ni网电极的SEM图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
本发明提供一种碱性电解水制氢用的膜电极,该膜电极包括多孔隔膜和分别负载于所述多孔隔膜两侧的析氢催化剂和析氧催化剂;所述多孔隔膜选自聚砜、聚醚砜、聚四氟乙烯、聚偏氟乙烯或聚苯硫醚多孔膜中的一种。本发明所述的膜电极采用更薄的高分子多孔隔膜,降低电解水的过电势,同时催化剂与隔膜形成牢固的粘结力,不易脱落,有助于提高膜电极电解水性能的稳定性。
根据本发明一种特别优选的实施方式,所述多孔隔膜孔隙率为30-80%,厚度为0.05-0.7mm;优选地,所述多孔隔膜孔隙率为50-70%,厚度为0.1-0.3mm;前述多孔隔膜膜电阻低,膜电导率高,能够降低碱性电解水的过电势。
根据本发明的一种优选实施方式,所述多孔隔膜还包括负载于所述多孔隔膜两侧的耐碱氧化物和/或氢氧化物涂层;负载耐碱氧化物涂层和/或氢氧化物涂层的多孔隔膜,改进隔膜的亲水性,进一步降低膜电极的电阻,提高膜电极电导率,有利于降低碱性电解水的过电势。
根据本发明的一种优选实施方式,所述耐碱氧化物和/或氢氧化物的金属选自IIA族、ⅣA族、IIB族、ⅣB族、VB族、ⅥB族、ⅦB族、Ⅷ族和稀土元素中的一种或多种,优选地,所述耐碱氧化物和/或氢氧化物的金属选自锆、钛、锰、锌和铈中的一种或多种;前述金属的耐碱氧化物和/或氢氧化物有利于进一步降低膜电极的电阻,提高膜电极电导率,有利于降低碱性电解水的过电势。
根据本发明的一种优选实施方式,所述耐碱氧化物和/或氢氧化物涂层厚度为0.05-10um;优选为1-5um;在该范围内的耐碱氧化物和/或氢氧化物涂层厚度,使所述膜电极具有膜电阻低的优点。
耐碱氧化物和/或氢氧化物用量为0.03-12mg/cm2;优选为3-10mg/cm2。
根据本发明的一种优选实施方式,耐碱氧化物和/或氢氧化物用量为0.03-12mg/cm2;优选为3-10mg/cm2;在该范围内的耐碱氧化物和/或氢氧化物用量,使所述膜电极具有膜电阻低的优点。
根据本发明,本发明对所述耐碱氧化物和/或氢氧化物涂层的负载方式没有特别的限定,优选地,所述耐碱氧化物或氢氧化物涂层通过涂布法或物理气相沉积法负载于所述多孔隔膜两侧。
根据本发明的一种优选实施方式,所述涂布法可以为自直接涂布法或转印涂布在多孔隔膜两侧涂布耐碱氧化物或氢氧化物涂层。优选地,涂布条件步骤包括制浆、涂布和转印步骤。
根据本发明的一种优选实施方式,所述物理气相沉积法可选自真空蒸镀、溅射镀膜、电弧等离子体镀、离子镀膜和分子束外延或磁控溅射法中的一种。
根据本发明,优选通过磁控溅射法将耐碱氧化物涂层负载于所述多孔隔膜两侧,优选地,该方法包括以下步骤:
将耐碱氧化物或氢氧化物制备成第一靶材,在真空条件下充入氩气,并在高压下使氩气进行辉光放电,形成氩离子,氩离子在电场力的作用下加速轰击靶材使第一靶材溅射出来,按照负载比例将第一靶材沉积到多孔隔膜上。使用磁控溅射法将耐碱氧化物涂层负载于所述多孔隔膜两侧有利于进一步降低膜电极的电阻,提高膜电极电导率,有利于降低碱性电解水的过电势。
根据本发明的一种优选实施方式,所述析氢催化剂的负载量为1-30mg/cm2;优选为10-20mg/cm2;该范围内的析氢催化剂负载量有利于进一步降低碱性电解水的过电势。
根据本发明的一种优选实施方式,所述析氧催化剂的负载量为1-30mg/cm2;优选为8-15mg/cm2;该范围内的析氧催化剂负载量有利于进一步降低碱性电解水的过电势。
根据本发明,所述析氢催化剂为本领域常规析氢催化剂,可选地,所述析氢催化剂包括镍基金属,优选地,所述析氢催化剂包括镍金属。
根据本发明,所述析氧催化剂为本领域常规析氧催化剂,可选地,所述析氧催化剂包括镍基金属和/或镍基金属氧化物,优选地,所述析氧催化剂包括镍金属和/或镍金属氧化物。
根据本发明的一种优选实施方式,所述析氢催化剂和析氧催化剂各自含有其它金属元素,所述其它金属元素选自IIB族、ⅣB族、ⅥB族、ⅦB族、Ⅷ族、ⅣA族和稀土金属中的一种或多种的金属元素;所述析氢催化剂和析氧催化剂包含所述其它金属元素有利于提高电极催化剂的活性,降低电解水的过电位。
根据本发明的一种优选实施方式,所述IIB族元素选自Zn。
根据本发明的一种优选实施方式,所述ⅣB族元素选自Ti和/或Zr。
根据本发明的一种优选实施方式,所述ⅥB族元素选自Cr、Mo和W中的一种或多种。
根据本发明的一种优选实施方式,所述ⅦB族元素选自Mn。
根据本发明的一种优选实施方式,所述Ⅷ族元素选自Fe和/或Co。
根据本发明的一种优选实施方式,所述ⅣA族选自Sn。
根据本发明的一种优选实施方式,所述稀土元素选自Ce和/或La。
根据本发明的一种优选实施方式,所述其它金属元素为Mo、W、Mn、Fe、Co、Zn、Ce和La中的一种或多种;采用前述助剂有利于提高电极催化剂的活性,降低电解水的过电位。
根据本发明的一种优选实施方式,所述其它金属元素为Fe和/或Co,更优选为Fe和Co,且Fe与Co的负载量比例为1:1-3。
根据本发明,其它金属元素与镍元素的质量比可选范围较宽,常用的质量比均可用于本发明,针对本发明,
析氢催化剂中,其它金属元素与镍元素的质量比为0-20:1;优选为1-10:1。
析氧催化剂中,其它金属元素与镍元素的质量比为0-20:1;优选为1-15:1。
具有本发明前述特征的膜电极均可实现本发明的目的,对制备方法无特殊要求,本发明提供一种所述膜电极的制备方法,该方法包括:析氢催化剂和析氧催化剂各自通过物理气相沉积法分别负载于多孔隔膜两侧。
根据本发明的一种优选实施方式,析氢催化剂和析氧催化剂通过磁控溅射法分别负载于多孔隔膜两侧;
优选地,该方法包括以下步骤:将析氢催化剂或析氧催化剂制备成第二靶材,在真空条件下充入氩气,并在高压下使氩气进行辉光放电形成氩离子,氩离子在电场力的作用下加速轰击第二靶材使第二靶材溅射出来,按照负载比例将第二靶材沉积到多孔隔膜上。通过磁控溅射法将析氢和析氧催化剂镀在高分子多孔隔膜两侧,催化剂分散度高,进一步降低电解水的过电位,且通过该方法制备的膜电极催化剂层非常牢固,不易脱落,有助于提高膜电极电解水性能的稳定性。
以下将通过实施例对本发明进行详细描述。以下实施例中,厚度通过游标卡尺量取,催化剂负载量通过称重差减法计算得到,电流密度由总电流除以反应面积获得。
析氢催化剂和析氧催化剂采购于国药化学股份有限公司的市售品。
以下实施例中,通过磁控溅射法镀析氢催化剂和析氧催化剂各自的方法包括:将析氢催化剂或析氧催化剂制备成靶材,在真空条件下充入氩气,并在高压下使氩气进行辉光放电,形成氩离子,氩离子在电场力的作用下加速轰击靶材,按照负载比例将靶材沉积到多孔隔膜上。
实施例1
以Zirfon多孔膜为隔膜,厚度为0.5mm,孔隙率为70%,在隔膜两侧用磁控溅射法分别镀上析氢催化剂和析氧催化剂。其中,析氢催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2。析氧催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2。将膜电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。
实施例2
以Zirfon多孔膜为隔膜,厚度为0.2mm,孔隙率为50%,在隔膜两侧用磁控溅射法分别镀上析氢催化剂和析氧催化剂。其中,析氢催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2。析氧催化剂为FeCoNi催化剂,铁负载量为6mg/cm2,镍负载量为4mg/cm2,钴负载量为3mg/cm2。将膜电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。
实施例3
以Zirfon多孔膜为隔膜,厚度为0.2mm,孔隙率为60%,在隔膜两侧用磁控溅射法分别镀上析氢催化剂和析氧催化剂。其中,析氢催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2。析氧催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2。将膜电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。
实施例4
以Zirfon多孔膜为隔膜,厚度为0.2mm,孔隙率为60%,在隔膜两侧用磁控溅射法镀上CeO2,CeO2负载量为4mg/cm2;接着,在隔膜两侧用磁控溅射法分别镀上析氢催化剂和析氧催化剂;其中,析氢催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg cm2;析氧催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2;将膜电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。膜电极的SEM图如图1所示。
实施例5
以PES多孔膜为隔膜,厚度为0.2mm,孔隙率为60%,在隔膜两侧用磁控溅射法镀上CeO2,CeO2负载量为9mg/cm2。在隔膜两面上用磁控溅射法镀析氢催化剂和析氧催化剂,其中,析氢催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg cm2;析氧催化剂为NiCo催化剂,镍负载量为12mg/cm2,钴负载量为1mg/cm2;将膜电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。
对比例1
以聚苯硫醚无纺布1mm为隔膜,阳极电极为镍网,阴极电极为喷涂Ni-Al合金的镍网,阴极电极使用前用10重量%NaOH溶液进行浸泡处理24h,并用去离子水清洗至溶液呈中性。将无纺布、阳极电极和阴极电极组装成电解池,测试其在0.4A/cm2电流密度下的电解水电压。实验结果见表1。膜电极的SEM图如图2所示。
由图1和图2可以看出实施例4的膜电极催化剂的形貌和粒径与对比例1中的商业镍网电极催化剂存在显著差别。
表1
通过表1的结果可以看出,与对比例1相比,本发明实施例1-5所述的膜电极具有更低的电解水过电位。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
1.一种碱性电解水制氢用的膜电极,其特征在于,该膜电极包括多孔隔膜和分别负载于所述多孔隔膜两侧的析氢催化剂和析氧催化剂;
所述多孔隔膜选自聚砜、聚醚砜、聚四氟乙烯、聚偏氟乙烯或聚苯硫醚多孔膜中的一种。
2.根据权利要求1所述的膜电极,其中,
所述多孔隔膜孔隙率为30-80%,厚度为0.05-0.7mm;
优选地,所述多孔隔膜孔隙率为50-70%,厚度为0.1-0.3mm。
3.根据权利要求1或2所述的膜电极,其中,
所述多孔隔膜还包括负载于所述多孔隔膜两侧的耐碱氧化物涂层和/或氢氧化物涂层;
优选地,所述耐碱氧化物和/或氢氧化物的金属选自IIA族、ⅣA族、IIB族、ⅣB族、VB族、ⅥB族、ⅦB族、Ⅷ族和稀土元素中的一种或多种。
4.根据权利要求3所述的膜电极,其中,
所述耐碱氧化物涂层和/或氢氧化物涂层厚度为0.05-20um;优选为1-5um;和/或
耐碱氧化物和/或氢氧化物用量为0.03-12mg/cm2;优选为3-10mg/cm2。
5.根据权利要求1-4中任意一项所述的膜电极,其中,
所述析氢催化剂的负载量为1-30mg/cm2;和/或
所述析氧催化剂的负载量为1-30mg/cm2。
6.根据权利要求1-5中任意一项所述的膜电极,其中,
所述析氢催化剂包括镍元素的金属;和/或
所述析氧催化剂包括镍元素的金属和/或金属氧化物。
7.根据权利要求1-6中任意一项所述的膜电极,其中,
所述析氢催化剂和析氧催化剂各自含有其他金属元素,所述其他金属元素选自IIB族、ⅣB族、ⅥB族、ⅦB族、Ⅷ族、ⅣA族和稀土元素中的一种或多种的金属元素。
8.根据权利要求7所述的膜电极,其中,
其他金属元素为Mo、W、Mn、Fe、Co、Zn、Ce和La中的一种或多种;和/或
析氢催化剂中,其他金属元素与镍元素的质量比为0-20:1;和/或
析氧催化剂中,其他金属元素与镍元素的质量比为0-20:1。
9.一种权利要求1-8中任意所述膜电极的制备方法,其特征在于,该方法包括:析氢催化剂和析氧催化剂各自通过物理气相沉积法分别负载于多孔隔膜两侧。
10.根据权利要求9所述的制备方法,其中,析氢催化剂和析氧催化剂的通过磁控溅射法分别负载于多孔隔膜两侧;
优选地,该方法包括以下步骤:将析氢催化剂或析氧催化剂制备成第二靶材,在真空条件下充入氩气,并在高压下使氩气进行辉光放电形成氩离子,氩离子在电场力的作用下加速轰击第二靶材使第二靶材溅射出来,按照负载比例将靶材沉积到多孔隔膜上。
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