CN107623131B - Preparation and application of membrane electrode based on platinum or platinum alloy nanotube - Google Patents

Preparation and application of membrane electrode based on platinum or platinum alloy nanotube Download PDF

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CN107623131B
CN107623131B CN201610553993.4A CN201610553993A CN107623131B CN 107623131 B CN107623131 B CN 107623131B CN 201610553993 A CN201610553993 A CN 201610553993A CN 107623131 B CN107623131 B CN 107623131B
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邵志刚
曾亚超
俞红梅
郭晓倩
宋微
张洪杰
衣宝廉
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明描述了一种基于铂或铂合金纳米管的膜电极的制备及应用,包括有序化电极微结构的形成,铂或铂合金纳米管的制备及膜电极的装配。首先在基底上生长具有规则取向的Co‑OH‑CO3纳米棒阵列,然后在此阵列上担载催化剂,并对担载有催化剂的Co‑OH‑CO3纳米棒阵列进行退火处理,最后将阵列热压于离子交换膜上得到膜电极,并对膜电极进行净化处理,所构建的膜电极可应用于燃料电池。本发明所构建的膜电极具有催化剂担载量低、催化剂利用率高、易于放大等优点。The invention describes the preparation and application of a membrane electrode based on platinum or platinum alloy nanotubes, including the formation of an ordered electrode microstructure, the preparation of platinum or platinum alloy nanotubes and the assembly of the membrane electrode. Firstly, regular orientation Co‑OH‑CO3 nanorod arrays are grown on the substrate, then catalysts are supported on the arrays, and the catalyst-loaded Co‑OH‑CO3 nanorod arrays are annealed. Finally, the arrays are heated The membrane electrode is obtained by pressing on the ion exchange membrane, and the membrane electrode is purified, and the constructed membrane electrode can be applied to a fuel cell. The membrane electrode constructed by the present invention has the advantages of low catalyst loading, high catalyst utilization rate, easy amplification and the like.

Description

基于铂或铂合金纳米管的膜电极的制备及其应用Preparation of Membrane Electrodes Based on Platinum or Platinum Alloy Nanotubes and Their Applications

技术领域technical field

本发明涉及一种膜电极的制备方法,属于燃料电池领域。The invention relates to a preparation method of a membrane electrode, belonging to the field of fuel cells.

背景技术Background technique

燃料电池是一种高效的能量转换装置,可有效地将存储于化学物质中的化学能转化为电能。目前,燃料电池已在电动汽车、分布式电站、航空等多个领域取得应用。质子交换膜燃料电池以其功率密度高、启动速度快、转换效率高、环境友好等优点受到广泛的关注。A fuel cell is an efficient energy conversion device that efficiently converts chemical energy stored in chemicals into electrical energy. At present, fuel cells have been applied in many fields such as electric vehicles, distributed power stations, and aviation. Proton exchange membrane fuel cells have attracted extensive attention due to their high power density, fast startup speed, high conversion efficiency, and environmental friendliness.

膜电极组件(MEA)是燃料电池电化学反应的核心部件,它由位于质子交换膜两侧的催化层和气体扩散层组成。膜电极主要分为气体扩散电极(Gas Diffusion Electrode,GDE)、薄层覆膜电极(catalyst coated membrane,CCM)和以美国3M公司的纳米薄层电极(nanostructured thin film,NSTF)为代表的有序化电极(ordered MEAs)。GDE采用丝网印刷、静电喷涂等工艺制备,将催化剂、憎水剂、有机溶剂组成催化剂浆料刷到气体扩散层上,经过高温处理后向催化层表面喷涂Naifon溶液实现电极立体化;CCM目前则普遍采用喷涂、转印等制备工艺,将催化剂、离子导体树脂和有机溶剂组成的浆料喷涂到膜上,或者先将浆料喷涂到其他载体上再转印到膜上,形成膜催化层一体化电极。传统的CCM电极、GDE电极的制备工艺成熟,但电极的催化层厚度大、催化剂呈无序堆积,使得催化剂的用量高、催化剂利用率低。为解决燃料电池贵重金属用量高、催化剂利用率低的问题,3M公司开发了一种有序薄层电极(NSTF electrode,Nanostructured Thin Film electrode),它具有微观有序、催化剂担载量低等特点,可有效降低传质阻力并提高催化剂的利用率。The membrane electrode assembly (MEA) is the core component of the electrochemical reaction of the fuel cell. It consists of a catalytic layer and a gas diffusion layer located on both sides of the proton exchange membrane. Membrane electrodes are mainly divided into gas diffusion electrodes (Gas Diffusion Electrode, GDE), thin-layer coated membrane electrodes (catalyst coated membrane, CCM) and ordered nano-thin layer electrodes (nanostructured thin film, NSTF) represented by 3M Company in the United States. ordered MEAs. GDE is prepared by screen printing, electrostatic spraying and other processes. The catalyst slurry composed of catalyst, hydrophobic agent and organic solvent is brushed onto the gas diffusion layer. After high temperature treatment, Naifon solution is sprayed on the surface of the catalytic layer to realize the electrode three-dimensionalization; CCM currently Generally, spraying, transfer printing and other preparation processes are used to spray the slurry composed of catalyst, ion conductor resin and organic solvent onto the membrane, or the slurry is first sprayed onto other carriers and then transferred to the membrane to form a membrane catalytic layer. Integrated electrode. The traditional CCM electrodes and GDE electrodes have mature preparation processes, but the thickness of the catalytic layer of the electrodes is large and the catalysts are stacked in disorder, which makes the amount of catalysts high and the utilization rate of catalysts low. In order to solve the problems of high consumption of precious metals and low catalyst utilization in fuel cells, 3M Company has developed an ordered thin film electrode (NSTF electrode, Nanostructured Thin Film electrode), which has the characteristics of microscopic order and low catalyst loading. , which can effectively reduce the mass transfer resistance and improve the utilization rate of the catalyst.

专利US5039561介绍了一种有序化纳米晶须阵列的制备方法,具体为在基底上沉积有机物薄膜,然后对有机物薄膜在高温、高真空条件下进行退火处理,得到高度有序的纳米晶须阵列。该发明所制备的纳米晶须阵列具有优异的化学稳定性和机械强度。Patent US5039561 introduces a method for preparing an ordered nanowhisker array, specifically depositing an organic thin film on a substrate, and then annealing the organic thin film under high temperature and high vacuum conditions to obtain a highly ordered nanowhisker array . The nanowhisker array prepared by the invention has excellent chemical stability and mechanical strength.

专利US20110151353A1介绍了一种NSTF电极的制备方法,具体为采用磁控溅射技术在有序化纳米晶须阵列上沉积Pt、Mn、Co、Ir等金属,然后将担载有催化剂的纳米棒阵列转印于离子交换膜的一侧或者两侧,所制备的电极适用于燃料电池、水电解池。该发明所制备的电极具有贵金属用量低、电化学活性高、稳定性好、传质阻力小等优点。Patent US20110151353A1 introduces a preparation method of NSTF electrodes, which is to deposit Pt, Mn, Co, Ir and other metals on the ordered nanowhisker array by magnetron sputtering technology, and then deposit the nanorod arrays loaded with catalysts Transferred to one or both sides of the ion exchange membrane, the prepared electrode is suitable for fuel cells and water electrolysis cells. The electrode prepared by the invention has the advantages of low noble metal dosage, high electrochemical activity, good stability, low mass transfer resistance and the like.

专利CN201310690828.X介绍了一种自支撑催化层的制备方法,具体为采用水热法制备有序化的纳米棒阵列,然后采用磁控溅射技术在阵列上担载催化剂,最后将催化剂转印到离子交换膜上。该专利所制备的电极具有担量低、厚度薄的特点,但是该专利所制备的催化层由铂和其它金属的机械混合物构成,是一种无序的大孔薄膜电极。Patent CN201310690828.X introduces a method for preparing a self-supporting catalytic layer, specifically preparing an ordered nanorod array by hydrothermal method, then using magnetron sputtering technology to support catalyst on the array, and finally transferring the catalyst onto the ion exchange membrane. The electrode prepared in this patent has the characteristics of low load and thin thickness, but the catalytic layer prepared in this patent is composed of a mechanical mixture of platinum and other metals, which is a disordered macroporous thin film electrode.

本发明在专利CN201310690828.X的基础上制备了基于铂及其合金纳米管的膜电极。所制备的电极由铂或者铂合金纳米管构成。所制备的电极的形貌、组成与专利CN201310690828.X不同。本发明所采用的方法条件温和、操作简单,可有效降低电极的贵金属用量。The invention prepares membrane electrodes based on platinum and its alloy nanotubes on the basis of patent CN201310690828.X. The prepared electrodes consist of platinum or platinum alloy nanotubes. The morphology and composition of the prepared electrodes are different from those of the patent CN201310690828.X. The method adopted in the present invention has mild conditions and simple operation, and can effectively reduce the amount of precious metal in the electrode.

发明内容SUMMARY OF THE INVENTION

一种基于铂或者铂合金纳米管的膜电极的制备方法,包括以下步骤:A method for preparing a membrane electrode based on platinum or platinum alloy nanotubes, comprising the following steps:

1)配制反应溶液;反应溶液为浓度为1-30mM的氟化铵,1-30mM的尿素,1-50mM的硝酸钴的水溶液;1) Prepare a reaction solution; the reaction solution is an aqueous solution of 1-30 mM ammonium fluoride, 1-30 mM urea, and 1-50 mM cobalt nitrate;

2)将基底浸渍入反应溶液中,在高压反应釜中90-150℃下反应30min-24h,在基底上制备得到Co-OH-CO3阵列;所采用的基底可为玻璃、镍片、镍网、不锈钢或者钛片;2) Immerse the substrate into the reaction solution, react in an autoclave at 90-150°C for 30min-24h, and prepare a Co-OH- CO3 array on the substrate; the substrate used can be glass, nickel sheet, nickel Mesh, stainless steel or titanium sheet;

3)在Co-OH-CO3阵列上担载催化剂,担载催化剂的方法有物理气相沉积、化学气相沉积,所担载的催化剂是Pt、Pd、Ru、Co、Ni、Fe、Cu、Au、Ag、Mn、Ir、Cr中的一种金属或者几种金属的合金,Pt与其他金属的原子比例为1:5~9:1;3) The catalyst is supported on the Co-OH-CO 3 array. The methods of supporting the catalyst include physical vapor deposition and chemical vapor deposition. The supported catalysts are Pt, Pd, Ru, Co, Ni, Fe, Cu, Au , a metal or an alloy of several metals among Ag, Mn, Ir, Cr, and the atomic ratio of Pt to other metals is 1:5 to 9:1;

4)对担载有催化剂的Co-OH-CO3阵列进行退火处理,退火温度为200℃~1000℃,退火气氛为H2,N2,Ar,He,或者H2-Ar、H2-N2、H2-He的混合气体,混合气体中H2的含量为1vol.%~99vol.%,退火时间为10min-7days;4) Perform annealing treatment on the Co-OH-CO 3 array loaded with catalyst, the annealing temperature is 200℃~1000℃, and the annealing atmosphere is H 2 , N 2 , Ar, He, or H 2 -Ar, H 2 - The mixed gas of N 2 and H 2 -He, the content of H 2 in the mixed gas is 1vol.%~99vol.%, and the annealing time is 10min-7days;

5)采用转印法将经过退火处理的阵列转印到离子交换膜的一侧或者两侧,移除基底;转印时施加压力大小为0.1~50MPa,时间在1s~30min,温度在20~200℃,所采用的离子交换膜为阳离子交换膜或者阴离子交换膜;5) Transfer the annealed array to one or both sides of the ion exchange membrane by the transfer method, and remove the substrate; the pressure applied during transfer is 0.1-50MPa, the time is 1s-30min, and the temperature is 20- 200℃, the ion exchange membrane used is a cation exchange membrane or an anion exchange membrane;

6)对转印有催化层的离子交换膜进行酸洗处理,酸洗可以选用HCl、H2SO4、HNO3或者HF溶液,酸浓度为1mM-10M,酸洗温度为20℃~100℃,酸洗时间为1min-24h;6) Pickling the ion-exchange membrane transferred with the catalytic layer, the pickling can be HCl, H 2 SO 4 , HNO 3 or HF solution, the acid concentration is 1mM-10M, and the pickling temperature is 20℃~100℃ , the pickling time is 1min-24h;

7)对经过酸洗的膜电极进行水洗,去除膜电极中残存的酸,水洗的温度为25℃~100℃,水洗时间为1min-24h;7) Wash the acid-washed membrane electrode with water to remove the acid remaining in the membrane electrode. The washing temperature is 25℃~100℃, and the washing time is 1min-24h;

8)将电极浸渍于过氧化氢的水溶液中,去除电极制备过程中引入的有机物,过氧化氢的质量浓度为1%~10%,浸渍的温度为25℃~100℃,浸渍时间为1min-24h;8) Immerse the electrode in an aqueous solution of hydrogen peroxide to remove organics introduced during the preparation of the electrode. The mass concentration of hydrogen peroxide is 1% to 10%, the immersion temperature is 25°C to 100°C, and the immersion time is 1min- 24h;

9)将电极置于20℃~100℃的硫酸溶液中煮30min~1h,硫酸的质量浓度在1wt.%~30wt.%;9) Put the electrode in the sulfuric acid solution of 20℃~100℃ and boil for 30min~1h, the mass concentration of sulfuric acid is 1wt.%~30wt.%;

10)对经过上述步骤的电极进行水洗,水洗温度为20℃~100℃,水洗时间为20s-24h。10) Washing the electrode after the above steps, the washing temperature is 20°C to 100°C, and the washing time is 20s-24h.

本发明具有如下特点:The present invention has the following characteristics:

1.本发明制备的膜电极的催化层由铂或者铂合金纳米管构成;1. The catalytic layer of the membrane electrode prepared by the present invention is composed of platinum or platinum alloy nanotubes;

2.本发明描述的电极制备方法具有制备条件温和、操作简单的特点;2. The electrode preparation method described in the present invention has the characteristics of mild preparation conditions and simple operation;

3.本发明制备的膜电极具有贵金属用量低、催化剂组分可调、催化层厚度薄的特点;3. The membrane electrode prepared by the present invention has the characteristics of low consumption of precious metals, adjustable catalyst components, and thin catalyst layer thickness;

4.全电池测试表明,基于铂或者铂合金纳米管膜电极具有高的质量比功率和催化剂利用率4. Full-cell tests show that the membrane electrodes based on platinum or platinum alloy nanotubes have high mass specific power and catalyst utilization

附图说明Description of drawings

图1为实施例1制备膜电极的流程图。FIG. 1 is a flow chart of the preparation of membrane electrodes in Example 1. FIG.

图2为实施例1所制备的Co-OH-CO3纳米棒阵列的扫描电镜图。2 is a scanning electron microscope image of the Co-OH-CO 3 nanorod array prepared in Example 1.

图3为实施例1所制备的铂纳米棒阵列的扫描电镜图。FIG. 3 is a scanning electron microscope image of the platinum nanorod array prepared in Example 1. FIG.

图4为实施例1所制备的膜电极的扫描电镜图。FIG. 4 is a scanning electron microscope image of the membrane electrode prepared in Example 1. FIG.

图5为实施例1所制备的膜电极的XRD图。FIG. 5 is an XRD pattern of the membrane electrode prepared in Example 1. FIG.

图6为实施例1所制备的膜电极在燃料电池中的I-V性能曲线。FIG. 6 is the I-V performance curve of the membrane electrode prepared in Example 1 in the fuel cell.

图7为实施例2所制备的铂钴纳米棒阵列的扫描电镜图。FIG. 7 is a scanning electron microscope image of the platinum-cobalt nanorod array prepared in Example 2. FIG.

图8为实施例2所制备的膜电极的扫描电镜图。FIG. 8 is a scanning electron microscope image of the membrane electrode prepared in Example 2. FIG.

图9为实施例2所制备的膜电极的XRD图。FIG. 9 is an XRD pattern of the membrane electrode prepared in Example 2. FIG.

图10为实施例2所制备的膜电极在燃料电池中的I-V性能曲线。FIG. 10 is the I-V performance curve of the membrane electrode prepared in Example 2 in the fuel cell.

图11为实施例3所制备的铂铁纳米棒阵列的扫描电镜图。FIG. 11 is a scanning electron microscope image of the platinum-iron nanorod array prepared in Example 3. FIG.

图12为实施例3所制备的膜电极的扫描电镜图。FIG. 12 is a scanning electron microscope image of the membrane electrode prepared in Example 3. FIG.

图13为实施例3所制备的膜电极的XRD图。FIG. 13 is the XRD pattern of the membrane electrode prepared in Example 3. FIG.

图14为实施例3所制备的膜电极在燃料电池中的I-V性能曲线。FIG. 14 is the I-V performance curve of the membrane electrode prepared in Example 3 in the fuel cell.

具体实施方式Detailed ways

以下实施例是对本发明的进一步说明,本发明同时保护明显变型方式和等同替代方式。The following examples are further illustrations of the invention, which protects both obvious modifications and equivalent alternatives.

实施例1Example 1

以不锈钢为基底,采用水热法制备Co-OH-CO3阵列。反应溶液为10mM的氟化铵,25mM的尿素,5mM的硝酸钴。在高压反应釜中120℃反应5h,在基底上制备成Co-OH-CO3阵列。图2所示为制备的Co-OH-CO3纳米棒阵列的扫描电镜图。由图可以看出Co-OH-CO3纳米棒阵列均匀地生长在基底上,生长方向基本垂直于基底。Co-OH-CO3纳米棒的长度约为3μm,直径约为100nm,Co-OH-CO3纳米棒的面密度为3~4e9/cm2Co-OH- CO3 arrays were prepared by a hydrothermal method using stainless steel as a substrate. The reaction solution was 10 mM ammonium fluoride, 25 mM urea, 5 mM cobalt nitrate. In an autoclave at 120 °C for 5 h, a Co-OH-CO 3 array was prepared on the substrate. Figure 2 shows the SEM images of the as-prepared Co-OH - CO nanorod arrays. It can be seen from the figure that the Co-OH- CO3 nanorod arrays are uniformly grown on the substrate, and the growth direction is substantially perpendicular to the substrate. The length of the Co-OH-CO 3 nanorods is about 3 μm, the diameter is about 100 nm, and the areal density of the Co-OH-CO 3 nanorods is 3-4e 9 /cm 2 .

采用磁控溅射方法在Co-OH-CO3阵列上担载Pt。磁控溅射功率为150W,溅射时间为10min,操作压力为1.0Pa。将担载有Pt的Co-OH-CO3阵列在300℃,H2-Ar(H2体积分数为5%)气氛下退火60min。图3所示为制备的纳米棒阵列的扫描电镜图。由图可以看出磁控溅射在Co-OH-CO3阵列上担载了均匀的Pt层,Pt层的厚度约为20nm。退火处理没有破坏阵列的有序性,担载有Pt的Co-OH-CO3纳米棒的长度约为2μm,直径约为140nm。Pt was supported on the Co-OH- CO3 array by magnetron sputtering method. The magnetron sputtering power was 150W, the sputtering time was 10min, and the operating pressure was 1.0Pa. The Pt-loaded Co-OH-CO 3 arrays were annealed at 300 °C in a H 2 -Ar (H 2 volume fraction of 5%) atmosphere for 60 min. Figure 3 shows the scanning electron microscope images of the fabricated nanorod arrays. It can be seen from the figure that the magnetron sputtering supports a uniform Pt layer on the Co-OH- CO3 array, and the thickness of the Pt layer is about 20 nm. The annealing treatment did not destroy the order of the array, and the Pt-loaded Co-OH- CO3 nanorods were about 2 μm in length and 140 nm in diameter.

将退火处理后的铂纳米棒阵列转印于离子交换膜的一侧,所采用的离子交换膜为

Figure BDA0001049242140000041
212膜。转印压力为4MPa,转印温度为140℃,转印时间为1min。ICP测试表明所制备的膜电极的铂担量为68.1μg cm-2。The annealed platinum nanorod array was transferred to one side of the ion-exchange membrane, and the ion-exchange membrane used was
Figure BDA0001049242140000041
212 film. The transfer pressure was 4MPa, the transfer temperature was 140°C, and the transfer time was 1min. The ICP test showed that the platinum loading of the prepared membrane electrode was 68.1 μg cm -2 .

移除不锈钢基底,对膜电极进行净化处理,处理流程为:将担载有催化层的离子交换膜置于0.5M的硫酸溶液中,去除作为模板的Co-OH-CO3阵列,将膜电极在去离子水中清洗,去除残存的酸液。将膜电极在80℃的0.5M硫酸溶液中煮30min,在去离子水中清洗掉残存的酸液,然后在80℃的5%的过氧化氢水溶液中煮30min,最后将电极80℃的去离子水中煮30min,将膜电极电极干燥后封装成膜电极组件。图4为所制备的膜电极的扫描电镜图,由图可以看出,所制备的催化层由纳米管构成,纳米管的直径为140nm,长度约为2μm,管壁厚度约为20nm。图5为所制备的电极的XRD图,由图可以看出磁控溅射制备的催化层由单一元素铂组成。The stainless steel substrate was removed, and the membrane electrode was purified. The treatment process was as follows: placing the ion exchange membrane carrying the catalytic layer in a 0.5M sulfuric acid solution, removing the Co-OH-CO 3 array as a template, and placing the membrane electrode in a 0.5M sulfuric acid solution. Rinse in deionized water to remove residual acid. The membrane electrode was boiled in a 0.5M sulfuric acid solution at 80°C for 30min, the residual acid was washed away in deionized water, and then boiled in a 5% aqueous hydrogen peroxide solution at 80°C for 30min, and finally the electrode was deionized at 80°C. Boil in water for 30 min, dry the membrane electrode and encapsulate it into a membrane electrode assembly. Figure 4 is a scanning electron microscope image of the prepared membrane electrode. It can be seen from the figure that the prepared catalytic layer is composed of nanotubes. The diameter of the nanotubes is 140 nm, the length is about 2 μm, and the thickness of the tube wall is about 20 nm. FIG. 5 is the XRD pattern of the prepared electrode, from which it can be seen that the catalytic layer prepared by magnetron sputtering is composed of a single element platinum.

将所制备的膜电极封装成膜电极组件,封装的压力为0.5MPa,温度为140℃。膜电极组件的阳极采用气体扩散电极,阳极Pt/C(70wt.%,Johnson Matthey)担量为0.2mg cm-2,电解质隔膜为

Figure BDA0001049242140000042
212膜。The prepared membrane electrode was packaged into a membrane electrode assembly, the packaging pressure was 0.5 MPa, and the temperature was 140 °C. The anode of the membrane electrode assembly adopts a gas diffusion electrode, the anode Pt/C (70wt.%, Johnson Matthey) load is 0.2mg cm -2 , and the electrolyte separator is
Figure BDA0001049242140000042
212 film.

电池测试条件:H2/O2流量:50/100sccm;电池温度75℃,饱和增湿,电池背压为0.2MPa。图6所示为基于铂纳米管的膜电极燃料电池中的I-V性能曲线,电池的最大输出功率为736mW cm-2。由图可以看出单电池的质量比功率高达2.745kW g-1Pt。Battery test conditions: H 2 /O 2 flow rate: 50/100sccm; battery temperature 75°C, saturated humidification, battery back pressure 0.2MPa. Figure 6 shows the IV performance curves in a platinum nanotube-based membrane electrode fuel cell with a maximum output of 736 mW cm -2 . It can be seen from the figure that the mass specific power of the single cell is as high as 2.745kW g -1 Pt.

实施例2Example 2

以不锈钢为基底,采用水热法制备Co-OH-CO3阵列。反应溶液为10mM的氟化铵,25mM的尿素,5mM的硝酸钴。在高压反应釜中120℃反应4h,在基底上制备成Co-OH-CO3阵列。Co-OH- CO3 arrays were prepared by a hydrothermal method using stainless steel as a substrate. The reaction solution was 10 mM ammonium fluoride, 25 mM urea, 5 mM cobalt nitrate. After reacting at 120 °C for 4 h in an autoclave, a Co-OH- CO3 array was prepared on the substrate.

采用磁控溅射方法在Co-OH-CO3阵列上担载PtCo(原子比为3:1)。磁控溅射功率为100W,溅射时间为20min,操作压力为1.0Pa。将担载有PtCo的Co-OH-CO3阵列在400℃,H2-Ar(H2体积分数为5%)气氛下退火1h。图7所示为制备的铂钴纳米管阵列的扫描电镜图。由图可以看出磁控溅射在Co-OH-CO3纳米棒阵列表面担载上了均匀的PtCo催化剂,PtCo镀层的厚度约为18nm,退火处理没有破坏阵列的有序性。担载有PtCo镀层的Co-OH-CO3纳米棒的长度约为3μm,直径约为136nm。PtCo ( 3 :1 atomic ratio) was supported on Co-OH-CO arrays by magnetron sputtering. The magnetron sputtering power was 100W, the sputtering time was 20min, and the operating pressure was 1.0Pa. The PtCo-loaded Co-OH- CO3 arrays were annealed at 400 °C in an H2 -Ar (5% H2 volume fraction) atmosphere for 1 h. Figure 7 shows the scanning electron microscope image of the prepared platinum cobalt nanotube array. It can be seen from the figure that the uniform PtCo catalyst is supported on the surface of the Co-OH-CO 3 nanorod array by magnetron sputtering. The thickness of the PtCo coating is about 18 nm, and the annealing treatment does not destroy the order of the array. The Co-OH-CO nanorods loaded with PtCo coating are about 3 μm in length and 136 nm in diameter.

将退火处理后的铂纳米棒阵列转印于离子交换膜的一侧,所采用的离子交换膜为

Figure BDA0001049242140000051
212膜。转印压力为0.5MPa,转印温度为150℃,转印时间为2min。ICP测试表明所制备的膜电极的Pt担量为40.15μg cm-2,Co担量为3.825μg cm-2。The annealed platinum nanorod array was transferred to one side of the ion-exchange membrane, and the ion-exchange membrane used was
Figure BDA0001049242140000051
212 film. The transfer pressure was 0.5MPa, the transfer temperature was 150°C, and the transfer time was 2min. The ICP test showed that the Pt loading of the prepared membrane electrode was 40.15 μg cm -2 and the Co loading was 3.825 μg cm -2 .

移除不锈钢基底,对膜电极进行净化处理,处理流程参见实施例1。图8为所制备的膜电极的扫描电镜图,由图可知PtCo纳米管的直径约为136nm,管壁厚度约为18nm,PtCo纳米管的长度约为2-3μm。图9为所制备的电极的XRD图。XRD测试表明,所制备的纳米管是PtCo合金纳米管,部分Pt原子与Co形成了合金。The stainless steel substrate was removed, and the membrane electrode was subjected to purification treatment. See Example 1 for the treatment flow. 8 is a scanning electron microscope image of the prepared membrane electrode. It can be seen from the figure that the diameter of the PtCo nanotube is about 136 nm, the thickness of the tube wall is about 18 nm, and the length of the PtCo nanotube is about 2-3 μm. FIG. 9 is an XRD pattern of the prepared electrode. XRD test shows that the prepared nanotubes are PtCo alloy nanotubes, and some Pt atoms form alloys with Co.

将所制备的膜电极封装成膜电极组件,封装的压力为0.5MPa,温度为140℃。膜电极组件的阳极采用气体扩散电极,阳极Pt/C(70wt.%,Johnson Matthey)担量为0.2mg cm-2,电解质隔膜为

Figure BDA0001049242140000052
212膜。电池测试条件:H2/O2流量:50/100sccm;电池温度75℃,饱和增湿,电池背压为0.2MPa。图10所示为基于铂钴纳米管阵列的膜电极燃料电池中的I-V性能曲线,电池的最大输出功率为685mWcm-2,由图可以看出单电池的质量比功率高达2.85kWg-1Pt。The prepared membrane electrode was packaged into a membrane electrode assembly, the packaging pressure was 0.5 MPa, and the temperature was 140 °C. The anode of the membrane electrode assembly adopts a gas diffusion electrode, the anode Pt/C (70wt.%, Johnson Matthey) load is 0.2mg cm -2 , and the electrolyte separator is
Figure BDA0001049242140000052
212 film. Battery test conditions: H 2 /O 2 flow rate: 50/100sccm; battery temperature 75°C, saturated humidification, battery back pressure 0.2MPa. Figure 10 shows the IV performance curve of the membrane electrode fuel cell based on platinum cobalt nanotube arrays. The maximum output power of the cell is 685mWcm -2 . It can be seen from the figure that the mass specific power of the single cell is as high as 2.85kWg -1 Pt.

实施例3Example 3

Co-OH-CO3阵列的制备方法参加实施例2。See Example 2 for the preparation method of Co-OH-CO 3 arrays.

采用磁控溅射方法在Co-OH-CO3阵列上担载PtFe(原子比例1:1)。磁控溅射功率为100W,溅射时间为20min,操作压力为1.0Pa。将担载有PtFe的Co-OH-CO3阵列在600℃,H2-Ar(H2体积分数为5%)气氛下退火1h。图11所示为制备的纳米棒阵列的扫描电镜图,由图可知所制备的PtFe纳米棒呈一定取向性垂直生长于基底上,担载有PtFe镀层的Co-OH-CO3纳米棒的长度约为2.5μm,直径约为130nm。PtFe (atomic ratio 1:1) was supported on Co-OH - CO arrays by magnetron sputtering. The magnetron sputtering power was 100W, the sputtering time was 20min, and the operating pressure was 1.0Pa. The PtFe-loaded Co-OH- CO3 arrays were annealed at 600 °C in a H2 -Ar (5% H2 volume fraction) atmosphere for 1 h. Figure 11 shows the scanning electron microscope image of the prepared nanorod array. It can be seen from the figure that the prepared PtFe nanorods grow vertically on the substrate with a certain orientation, and the length of the Co-OH - CO nanorods carrying the PtFe coating is About 2.5μm, about 130nm in diameter.

膜电极的制备流程参见实施例2。图12为所制备的膜电极的扫描电镜图,由图可知所制备的催化层由PtFe纳米管构成,纳米管的直径约为130nm,管壁厚度约为15nm,长度约为1-2.5μm。ICP测试表明所制备的膜电极的Pt的担载量为49.735μg cm-2,Fe的担载量为1.875μg cm-2。图13为所制备的电极的XRD图谱,其中PtFe的衍射峰位置位于PtCo合金和PtFe合金的峰位置之间,表明所制备的电极是一种PtFe的合金。Refer to Example 2 for the preparation process of the membrane electrode. 12 is a scanning electron microscope image of the prepared membrane electrode. It can be seen from the figure that the prepared catalytic layer is composed of PtFe nanotubes. The diameter of the nanotubes is about 130 nm, the thickness of the tube wall is about 15 nm, and the length is about 1-2.5 μm. The ICP test showed that the Pt loading of the prepared membrane electrode was 49.735 μg cm -2 and the Fe loading was 1.875 μg cm -2 . 13 is the XRD pattern of the prepared electrode, wherein the diffraction peak position of PtFe is located between the peak positions of PtCo alloy and PtFe alloy, indicating that the prepared electrode is a PtFe alloy.

将所制备的膜电极封装成膜电极组件,封装的压力为0.5MPa,温度为140℃。膜电极组件的阳极采用气体扩散电极,阳极Pt/C(70wt.%,Johnson Matthey)担量为0.2mg cm-2,电解质隔膜为

Figure BDA0001049242140000053
212膜。电池测试条件:H2/O2流量:50/100sccm;电池温度75℃,饱和增湿,电池背压为0.2MPa。图14所示为基于PtFe纳米管的膜电极燃料电池中的I-V性能曲线,电池的最大输出功率为830mW cm-2,电池的质量比功率为3.32kW g-1Pt。The prepared membrane electrode was packaged into a membrane electrode assembly, the packaging pressure was 0.5 MPa, and the temperature was 140 °C. The anode of the membrane electrode assembly adopts a gas diffusion electrode, the anode Pt/C (70wt.%, Johnson Matthey) load is 0.2mg cm -2 , and the electrolyte separator is
Figure BDA0001049242140000053
212 film. Battery test conditions: H 2 /O 2 flow rate: 50/100sccm; battery temperature 75°C, saturated humidification, battery back pressure 0.2MPa . Figure 14 shows the IV performance curve in the PtFe nanotube-based membrane electrode fuel cell, the maximum output power of the cell is 830mW cm -2 , and the mass specific power of the cell is 3.32kW g -1 Pt.

Claims (7)

1. A membrane electrode based on platinum alloy nanotubes is characterized in that: the catalyst layer of the membrane electrode is composed of platinum alloy nanotubes which are annealed, and the prepared catalyst layer is positioned on one side or two sides of the ion exchange membrane; the tube wall of the nanotube is of an open structure;
the catalyst layer is composed of platinum alloy nanotubes with the diameter of 10 nm-200 nm and the length of 50 nm-5 mu m, the thickness of the catalyst layer is 50 nm-10 mu m, and the adopted ion exchange membrane is a cation exchange membrane or an anion exchange membrane;
the transition metal other than platinum, which constitutes the platinum alloy, is one or more of Fe, Co, Ni, Cu, Au, Ru, Pd, Ir, Mn, Cr and Ag, and the atomic ratio of platinum to transition metal is 1:5 to 9: 1.
2. A method for producing the membrane electrode of claim 1, characterized in that:
(1) growing Co-OH-CO vertical to substrate on substrate by hydrothermal method3A nanorod array;
(2) in the presence of Co-OH-CO3The nano-rods uniformly support a metal catalyst;
(3) Co-OH-CO loaded with catalyst3Carrying out annealing treatment on the array;
(4) transferring the nanorod array loaded with the catalyst to one side or two sides of the ion exchange membrane;
(5) and (5) purifying the membrane electrode.
3. The method for producing a membrane electrode according to claim 2, wherein: the substrate in the step (1) is glass, a nickel sheet, a nickel net, a stainless steel sheet or a titanium sheet;
Co-OH-CO in step (1)3The growth of the array is prepared by a high pressure hydrothermal method, comprising the following steps:
A. preparing a reaction solution, wherein the reaction solution is an aqueous solution containing 1-30mM of ammonium fluoride, 1-30mM of urea and 1-50mM of cobalt nitrate;
B. soaking the substrate in the reaction solution in a high-pressure reaction kettle for 90-150 timesoReacting for 30min-24h under C to prepare Co-OH-CO on the substrate3And (4) array.
4. The method for producing a membrane electrode according to claim 2, wherein: the method for supporting the catalyst in the step (2) comprises physical vapor deposition or chemical vapor deposition;
the catalyst carried in the step (2) is a platinum alloy, the catalyst is composed of Pt or platinum and one or more than two elements of Fe, Co, Ni, Cu, Au, Pd, Ru, Ir, Mn, Cr and Ag, the atomic ratio of platinum to other metals is 1: 5-9: 1, and the catalyst loading is 1 mu g cm-2~5 mg cm-2
5. The method for producing a membrane electrode according to claim 2, wherein: the annealing temperature in the step (3) is 200-1000 ℃, and the annealing atmosphere is H2、N2Ar, He, or H2-Ar、 H2-N2、H2Mixed gas of-He and H in the mixed gas2The content of (1) vol% to 99 vol%, and the annealing time is 10min to 7 days;
in the step (4), the pressure applied during transfer printing is 0.1-50 MPa, the time is 1 s-30 min, and the temperature is 20-200 ℃.
6. The method for producing a membrane electrode according to claim 2, wherein: the membrane electrode purification step in the step (5) is as follows:
(1) pickling the washed membrane electrode; the adopted acid is nitric acid, sulfuric acid or hydrochloric acid, the concentration is 5 mM-10M, the acid treatment temperature is 20-100 ℃, and the acid treatment time is 1min-24 h;
(2) washing the membrane electrode after acid washing with water at the temperature of 20-100 ℃;
(3) cleaning the membrane electrode in a hydrogen peroxide aqueous solution; the mass concentration of the hydrogen peroxide is 1-10%, and the cleaning temperature is 20-100 ℃;
(4) placing the membrane electrode in sulfuric acid solution for cleaning; the mass concentration of the sulfuric acid is 1-30 wt%, and the cleaning temperature is 20-100 ℃;
(5) and (3) cleaning the membrane electrode in deionized water at the temperature of 20-100 ℃.
7. Use of a membrane electrode according to claim 1, characterized in that: the prepared electrode is used for a fuel cell.
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