WO2021114056A1 - Fuel cell cathode catalyst and preparation method therefor, membrane electrode and fuel cell - Google Patents

Fuel cell cathode catalyst and preparation method therefor, membrane electrode and fuel cell Download PDF

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WO2021114056A1
WO2021114056A1 PCT/CN2019/124139 CN2019124139W WO2021114056A1 WO 2021114056 A1 WO2021114056 A1 WO 2021114056A1 CN 2019124139 W CN2019124139 W CN 2019124139W WO 2021114056 A1 WO2021114056 A1 WO 2021114056A1
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fuel cell
alloy nanoparticles
cathode catalyst
platinum alloy
platinum
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PCT/CN2019/124139
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French (fr)
Chinese (zh)
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高正飞
王中奇
史曦伶
王恒
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青岛创启新能催化科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the technical field of fuel cells, in particular to a fuel cell cathode catalyst and a preparation method thereof, a membrane electrode and a fuel cell.
  • Proton exchange membrane fuel cell is a fuel cell that converts chemical energy into electricity through cold combustion of hydrogen, with water as the only emission.
  • PEMFC is the core of hydrogen energy economy.
  • the cathode oxygen reduction reaction has a high overpotential and requires a precious metal platinum catalyst to achieve efficient use of hydrogen energy. Reducing the amount of platinum in the cathode catalyst is the key to achieving large-scale commercial applications of PEMFC.
  • the alloying of platinum with 3d transition metals has been proven to be an effective means to reduce the amount of platinum.
  • platinum alloy nanoparticles are deposited on a carbon support. However, in the traditional preparation method, the platinum alloy is not uniformly distributed on the carbon support, resulting in poor performance of the catalyst and limiting the application of this catalyst.
  • a preparation method of a fuel cell cathode catalyst includes the following steps:
  • the carbon carrier and the aqueous solution of the protective agent are uniformly mixed, and then platinum alloy nanoparticles are deposited to obtain a carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles include platinum and at least one 3d transition metal; and
  • the temperature of the first heat treatment is 500°C to 1000°C, and the time is 2h-10h; the temperature of the second heat treatment is 100°C to 300°C, and the time is 2h-10h.
  • the protective agent is sodium acetate or cetyltrimethylammonium bromide.
  • the molar ratio of the metal ions in the solution to the protective agent is 0.05 to 1.5.
  • the platinum alloy nanoparticles include a platinum alloy core and a platinum shell wrapped on the surface of the platinum alloy core;
  • the thickness of the platinum shell is 0.5 nm to 1.5 nm;
  • the platinum alloy core accounts for 40% to 75% of the platinum alloy nanoparticles by mass
  • the platinum alloy nanoparticles are selected from at least one of platinum-cobalt alloy nanoparticles, platinum-nickel alloy nanoparticles and platinum-iron alloy nanoparticles;
  • the mass fraction of the platinum alloy nanoparticles in the cathode catalyst of the fuel cell is 30%-50%;
  • the molar ratio of platinum to 3d transition metal is 1:3 to 5:1.
  • the operation of performing the first heat treatment on the carbon support deposited with platinum alloy nanoparticles is:
  • the carbon carrier deposited with platinum alloy nanoparticles is uniformly mixed with a nitrogen-containing compound, and then heat treated in an inert gas atmosphere at 500°C to 1000°C for 2h-10h to obtain a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles.
  • the mass fraction of nitrogen in the nitrogen-doped carbon carrier is 1%-30%
  • the size of the nitrogen-doped carbon support is 100 nm to 25 ⁇ m, and the specific surface area of the nitrogen-doped carbon support is 200 m 2 /g to 1500 m 2 /g.
  • the temperature of the first heat treatment is 600°C to 800°C and the time is 2h-6h; the temperature of the second heat treatment is 150°C to 250°C and the time is 1h-8h.
  • a fuel cell cathode catalyst is prepared by the above-mentioned method for preparing a fuel cell cathode catalyst.
  • a membrane electrode is also provided, including the above-mentioned fuel cell cathode catalyst.
  • a fuel cell is also provided, including the above-mentioned membrane electrode.
  • the platinum alloy nanoparticles are deposited after the carbon support and the protective agent are uniformly mixed, and the first heat treatment, acid treatment and second heat treatment are carried out in sequence. After the second heat treatment, in the fuel cell cathode catalyst obtained, platinum alloy nanoparticles are uniformly dispersed on the carbon support, and the fuel cell cathode catalyst has good catalytic activity, which is favorable for application.
  • the fuel cell cathode catalyst prepared by the above preparation method has excellent catalytic activity and stability, and is beneficial to industrial application.
  • Fig. 1 is a flow chart of a method for preparing a fuel cell cathode catalyst according to an embodiment of the present invention
  • Example 2 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Example 1;
  • Figure 3 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Example 2;
  • TEM 4 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Comparative Example 1.
  • the inventor of the present invention discovered during the research that the performance of the fuel cell catalyst is mainly affected by the surface structure and composition distribution of the catalyst, and the main obstacle to its progress is that it is difficult to achieve precise regulation of element distribution at the nano-level.
  • the present invention provides a method for preparing a fuel cell cathode catalyst, which improves the catalytic activity of the fuel cell cathode catalyst by improving the uniformity of the dispersion of platinum alloy nanoparticles on the carbon carrier.
  • a method for preparing a fuel cell cathode catalyst according to an embodiment of the present invention includes the following steps:
  • the carbon support includes but is not limited to conductive materials such as carbon nanotubes, carbon nanofibers, mesoporous carbon, carbon spheres, or graphene.
  • step S10 after the aqueous solution of the carbon carrier and the protective agent are mixed, the uniform dispersion of the two can be achieved by means such as stirring, ultrasonic dispersion and the like.
  • the protective agent is sodium acetate or cetyltrimethylammonium bromide. Tests have shown that these kinds of protective agents can improve the uniformity of the dispersion of platinum alloy nanoparticles on the carbon support, thereby improving the catalytic activity of the fuel cell cathode catalyst.
  • the protective agent is sodium acetate or cetyltrimethylammonium bromide
  • the protective agent is first dissolved in water, and then the carbon carrier is added to the aqueous solution of the protective agent and mixed uniformly. Experiments have proved that this is more beneficial to improve the uniformity of the dispersion of platinum alloy nanoparticles on the carbon support.
  • the molar ratio of the metal ions in the solution to the protective agent is 0.05 to 1.5. Tests have proved that after the metal ions and the protective agent in the above proportion are evenly mixed, the dispersion uniformity of the platinum alloy nanoparticles on the carbon support is improved, thereby improving the catalytic activity of the fuel cell cathode catalyst.
  • step S10 the operation of depositing platinum alloy nanoparticles is: adding the platinum precursor and at least one 3d transition metal precursor to the dispersion of the carbon carrier and the protective agent, mixing uniformly, and then adding the reducing agent to fully react to obtain .
  • the purpose of adding the reducing agent is to reduce the metal salt.
  • the reducing agent may be sodium borohydride, ascorbic acid or citric acid, for example.
  • the 3d transition metal refers to the metal in which the last electron of the atom is arranged on the 3d orbital.
  • metals such as cobalt, nickel, and iron.
  • the platinum alloy nanoparticles include a platinum alloy core and a platinum shell wrapped on the surface of the platinum alloy core.
  • the thickness of the platinum shell is 0.5 nm to 1.5 nm.
  • the platinum alloy core accounts for 40%-75% of the platinum alloy nanoparticles by mass.
  • the platinum alloy nanoparticles are selected from at least one of platinum-cobalt alloy nanoparticles, platinum-nickel alloy nanoparticles and platinum-iron alloy nanoparticles.
  • the platinum alloy nanoparticles further include one or two of manganese, iridium, rhodium, niobium and zirconium.
  • the particle size of platinum alloy nanoparticles ranges from 3 nm to 6 nm.
  • the mass fraction of platinum alloy nanoparticles in the cathode catalyst of the fuel cell is 30%-50%.
  • the molar ratio of platinum to the 3d transition metal is 1:3 to 5:1. Tests have proved that this is beneficial to improve the stability of the catalyst.
  • the operation of performing the first heat treatment on the carbon support deposited with platinum alloy nanoparticles is:
  • the carbon carrier deposited with platinum alloy nanoparticles is uniformly mixed with a nitrogen-containing compound, and then heat-treated in an inert gas atmosphere at 500°C to 1000°C for 2h-10h to obtain a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles.
  • the above-mentioned embodiment can obtain a nitrogen-doped carbon carrier loaded with platinum alloy nanoparticles.
  • the introduction of nitrogen atoms into the sp2 hybrid structure can not only greatly improve the electronic properties, surface alkalinity and other physical and chemical properties of the carbon material, but also the nitrogen-containing groups can increase the active sites of the carbon material surface to adsorb metal particles, and Stabilize the metal nanoparticles, thereby facilitating the acquisition of highly dispersible metal-supported catalysts.
  • the step of uniformly mixing the carbon carrier deposited with platinum alloy nanoparticles and the nitrogen-containing compound it further includes a step of acid-treating the carbon carrier deposited with platinum alloy nanoparticles.
  • the purpose is to activate the carbon support and platinum alloy particles simultaneously and consume 3d transition metals.
  • the mass fraction of nitrogen in the nitrogen-doped carbon carrier is 1%-30%;
  • the size of the nitrogen-doped carbon support is 100 nm-25 ⁇ m, and the specific surface area of the nitrogen-doped carbon support is 200 m 2 /g-1500 m 2 /g.
  • the stability of the carbon support can be optimized under the premise of ensuring the catalyst loading.
  • step S20 acid treatment refers to immersing the nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles in an acid solution, and then taking it out after maintaining it for a period of time. Among them, the process of soaking can be stirred.
  • the acid treatment is beneficial to consume the 3d transition metal on the surface of the platinum alloy nanoparticles and improve the stability of the alloy catalyst.
  • the acid used in the acid treatment is preferably at least one of acetic acid, sulfuric acid, nitric acid, and perchloric acid.
  • the pH of the acid treatment environment is less than 1
  • the temperature of the acid treatment is 50°C to 80°C
  • the time of the acid treatment is 1 hour to 12 hours.
  • the surface defects of the catalyst can be reduced, and the distribution of platinum on the surface of the catalyst can be increased, making it easier to combine with the nitrogen-doped carbon support, thereby improving stability.
  • Both the first heat treatment and the second heat treatment can be performed in an inert gas atmosphere or an oxygen-containing atmosphere.
  • the temperature of the first heat treatment is 600°C to 800°C and the time is 2h-6h; the temperature of the second heat treatment is 150°C to 250°C and the time is 1h-8h.
  • the platinum alloy nanoparticles are deposited after the carbon support and the protective agent are mixed uniformly, and the first heat treatment, acid treatment and second heat treatment are carried out in sequence. After the second heat treatment, in the fuel cell cathode catalyst obtained, platinum alloy nanoparticles are uniformly dispersed on the carbon support, and the fuel cell cathode catalyst has good catalytic activity, which is favorable for application.
  • the fuel cell cathode catalyst of one embodiment is prepared by the above-mentioned method for preparing the fuel cell cathode catalyst.
  • the fuel cell cathode catalyst prepared by the above preparation method has excellent catalytic activity and stability, and is beneficial to industrial application.
  • the membrane electrode of one embodiment includes the above-mentioned fuel cell cathode catalyst.
  • the fuel cell of one embodiment includes the above-mentioned membrane electrode.
  • the dried powder was heat-treated for the first time at 400°C for 2 hours, and the system was allowed to cool naturally after the end.
  • Prepare 10ml sulfuric acid solution with a concentration of 0.5mol/L add it to the flask, place it in a 70°C oil bath for acid treatment for 24h, after the reaction is over, wash with deionized water by centrifugation, and finally place it in a vacuum drying oven to dry.
  • the dried powder was placed at 400° C. for a second heat treatment for 2 hours, and the system was naturally cooled after the end, and the fuel cell cathode catalyst of Example 1 was obtained.
  • Example 1 The difference from Example 1 is that the protective agent is CTAB (hexadecyl trimethyl ammonium bromide), and the added amount is 75 mg.
  • CTAB hexadecyl trimethyl ammonium bromide
  • the dried powder was heat-treated for the first time at 700°C in an ammonia atmosphere for 4 hours, after which the system was allowed to cool naturally.
  • Prepare 10ml of sulfuric acid solution with a concentration of 0.5mol/L add it to the flask, and place it in a 70°C oil bath for acid treatment for 2h. After the reaction is over, wash with deionized water by centrifugation, and finally place it in a vacuum drying oven to dry.
  • the dried powder was placed at 250° C. for a second heat treatment for 1 hour, and the system was left to cool naturally after the end, and the fuel cell cathode catalyst of Example 3 was obtained.
  • Example 1 The difference from Example 1 is that the temperature of the first heat treatment is 600°C and the time is 3 hours; the temperature of the second heat treatment is 150°C and the time is 1 hour.
  • Example 5 Membrane Electrode (MEA)
  • Cathode ink preparation Add 400mg of the fuel cell cathode catalyst prepared in Example 1 into a glass bottle, mix well with 10g deionized water (Milli-Q), 15mg isopropanol (IPA), 4.5ml 5wt% Nafion solution (D520) , Get the cathode ink.
  • Anode ink preparation The HiSPEC4000 catalyst produced by Johnson Matthey is prepared into a uniform suspension using a method similar to the above.
  • MEA preparation (CCM mode): Using ultrasonic spraying equipment (USI product, Prism 4000 type), the above cathode ink and anode ink are respectively coated on both sides of the proton exchange membrane (Nafion 212), the area of the catalyst layer is 5cm 2 , quantitative controls were anode Pt loading 0.1mg / cm 2, the cathode 0.4mg / cm 2.
  • Example 1 The difference from Example 1 is that no sodium acetate is added.
  • Example 1 The fuel cell cathode catalysts prepared in Example 1, Example 2 and Comparative Example 1 were characterized by scanning electron microscopy, and Figure 2, Figure 3, and Figure 4 were obtained, respectively. From the comparison of Figure 2, Figure 3 and Figure 4, it can be seen that in the fuel cell cathode catalyst prepared in Example 1 and Example 2, platinum nickel nanoparticles are uniformly dispersed on the carbon support, indicating that the preparation method of the present application improves The uniformity of the platinum alloy nanoparticles on the carbon support is described.
  • Example 1 The fuel cell cathode catalysts of Example 1, Example 2 and Comparative Example 1 were tested for electrochemical surface area, specific activity, mass activity and stability respectively.
  • the test process is as follows:
  • the CV test conditions 0.1M HClO4 electrolyte of a saturated aqueous solution of N 2, with respect to The potential range of the reversible hydrogen electrode is 0.05V ⁇ 1.1V, and the scanning speed is 100mV/s; the oxygen reduction test condition is that the electrolyte is a 0.1M HClO 4 aqueous solution saturated with O 2 and the potential range of the reversible hydrogen electrode is 0.05V ⁇ 1.1V. The scanning speed is 20mV/s.
  • the fuel cell cathode catalysts of Example 1 and Example 2 have higher electrochemical surface area, specific activity, mass activity and stability. It shows that in the fuel cell cathode catalysts of Example 1 and Example 2, the platinum alloy nanoparticles supported on the surface of the carbon support are more stable and arranged more regular, so that the catalytic activity and stability are both better.

Abstract

The present invention relates to a fuel cell cathode catalyst and a preparation method therefor, a membrane electrode, and a fuel cell. The method for preparing the fuel cell cathode catalyst comprises the following steps: uniformly mixing a carbon carrier with an aqueous solution of a protective agent, and then depositing platinum alloy nanoparticles to obtain a carbon carrier deposited with the platinum alloy nanoparticles, wherein the platinum alloy nanoparticles comprise platinum and at least one 3d transition metal; and subjecting the carbon carrier deposited with the platinum alloy nanoparticles to a first heat treatment, an acid treatment and a second heat treatment in sequence to obtain the fuel cell cathode catalyst, wherein the first heat treatment has a temperature of 500°C to 1000°C and a time of 2 to 10 h, and the second heat treatment has a temperature of 100°C to 300°C and a time of 2 to 10 h. It has been found through tests that in the fuel cell cathode catalyst obtained by means of the above-mentioned method for preparing a fuel cell cathode catalyst of the present invention, the platinum alloy nanoparticles are uniformly dispersed on the carbon carrier, and the catalytic activity of the fuel cell cathode catalyst is relatively good, so that same facilitates application.

Description

燃料电池阴极催化剂及其制备方法、膜电极及燃料电池Cathode catalyst of fuel cell and preparation method thereof, membrane electrode and fuel cell 技术领域Technical field
本发明涉及燃料电池技术领域，特别是涉及一种燃料电池阴极催化剂及其制备方法、膜电极及燃料电池。The invention relates to the technical field of fuel cells, in particular to a fuel cell cathode catalyst and a preparation method thereof, a membrane electrode and a fuel cell.
背景技术Background technique
质子交换膜燃料电池(PEMFC，proton exchange membrane fuel cell)是一种燃料电池，通过氢气冷燃烧将化学能转化为电能，水是唯一排放物。PEMFC是氢能经济的核心，其阴极氧还原反应的过电势较高，需要贵金属铂催化剂，从而实现氢能的高效利用。降低阴极催化剂的铂用量是实现PEMFC大规模商业应用的关键，铂与3d过渡金属的合金化已被证明是减少铂用量的有效手段。传统的燃料电池阴极催化剂的制备方法中，将铂合金纳米颗粒沉积于碳载体上。然而，传统的制备方法中，铂合金在碳载体上的分布不均匀，导致催化剂的性能不佳，限制了这种催化剂的应用。Proton exchange membrane fuel cell (PEMFC, proton exchange membrane fuel cell) is a fuel cell that converts chemical energy into electricity through cold combustion of hydrogen, with water as the only emission. PEMFC is the core of hydrogen energy economy. The cathode oxygen reduction reaction has a high overpotential and requires a precious metal platinum catalyst to achieve efficient use of hydrogen energy. Reducing the amount of platinum in the cathode catalyst is the key to achieving large-scale commercial applications of PEMFC. The alloying of platinum with 3d transition metals has been proven to be an effective means to reduce the amount of platinum. In the traditional preparation method of fuel cell cathode catalyst, platinum alloy nanoparticles are deposited on a carbon support. However, in the traditional preparation method, the platinum alloy is not uniformly distributed on the carbon support, resulting in poor performance of the catalyst and limiting the application of this catalyst.
发明内容Summary of the invention
基于此，有必要针对如何提高催化剂的催化活性的问题，提供一种燃料电池阴极催化剂及其制备方法、膜电极及燃料电池。Based on this, it is necessary to provide a fuel cell cathode catalyst and a preparation method thereof, a membrane electrode and a fuel cell for the problem of how to improve the catalytic activity of the catalyst.
一种燃料电池阴极催化剂的制备方法，包括如下步骤：A preparation method of a fuel cell cathode catalyst includes the following steps:
将碳载体与保护剂的水溶液混合均匀，之后沉积铂合金纳米颗粒，得到沉积有铂合金纳米颗粒的碳载体；其中，所述铂合金纳米颗粒包括铂和至少一种3d过渡金属；以及The carbon carrier and the aqueous solution of the protective agent are uniformly mixed, and then platinum alloy nanoparticles are deposited to obtain a carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles include platinum and at least one 3d transition metal; and
对所述沉积有铂合金纳米颗粒的碳载体依次进行第一次热处理、酸处理以及第二次热处理，得到燃料电池阴极催化剂；Performing a first heat treatment, an acid treatment and a second heat treatment on the carbon support deposited with platinum alloy nanoparticles in sequence to obtain a fuel cell cathode catalyst;
其中，第一次热处理的温度为500℃～1000℃，时间为2h～10h；第二次热处理的温度为100℃～300℃，时间为2h～10h。Among them, the temperature of the first heat treatment is 500°C to 1000°C, and the time is 2h-10h; the temperature of the second heat treatment is 100°C to 300°C, and the time is 2h-10h.
在其中一个实施例中，所述保护剂为乙酸钠或者十六烷基三甲基溴化铵。In one of the embodiments, the protective agent is sodium acetate or cetyltrimethylammonium bromide.
在其中一个实施例中，沉积铂合金纳米颗粒的操作中，溶液中的金属离子与所述保护剂的摩尔比为0.05～1.5。In one of the embodiments, in the operation of depositing platinum alloy nanoparticles, the molar ratio of the metal ions in the solution to the protective agent is 0.05 to 1.5.
在其中一个实施例中，所述铂合金纳米颗粒包括铂合金核和包裹在所述铂合金核表面的铂壳；In one of the embodiments, the platinum alloy nanoparticles include a platinum alloy core and a platinum shell wrapped on the surface of the platinum alloy core;
所述铂壳的厚度为0.5nm～1.5nm；The thickness of the platinum shell is 0.5 nm to 1.5 nm;
所述铂合金核占所述铂合金纳米颗粒的质量分数为40％～75％；The platinum alloy core accounts for 40% to 75% of the platinum alloy nanoparticles by mass;
优选地，铂合金纳米颗粒选自铂钴合金纳米颗粒、铂镍合金纳米颗粒和铂铁合金纳米颗粒中的至少一种；Preferably, the platinum alloy nanoparticles are selected from at least one of platinum-cobalt alloy nanoparticles, platinum-nickel alloy nanoparticles and platinum-iron alloy nanoparticles;
优选地，所述铂合金纳米颗粒占所述燃料电池阴极催化剂的质量分数为30％～50％；Preferably, the mass fraction of the platinum alloy nanoparticles in the cathode catalyst of the fuel cell is 30%-50%;
优选地，所述铂合金纳米颗粒中，铂与3d过渡金属的摩尔比为1:3～5:1。Preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to 3d transition metal is 1:3 to 5:1.
在其中一个实施例中，对所述沉积有铂合金纳米颗粒的碳载体进行第一次热处理的操作为：In one of the embodiments, the operation of performing the first heat treatment on the carbon support deposited with platinum alloy nanoparticles is:
将所述沉积有铂合金纳米颗粒的碳载体与含氮化合物混合均匀，之后在惰性气体氛围中500℃～1000℃时热处理2h～10h，得到沉积有铂合金纳米颗粒的掺氮碳载体。The carbon carrier deposited with platinum alloy nanoparticles is uniformly mixed with a nitrogen-containing compound, and then heat treated in an inert gas atmosphere at 500°C to 1000°C for 2h-10h to obtain a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles.
在其中一个实施例中，所述掺氮碳载体中氮的质量分数为1％～30％；In one of the embodiments, the mass fraction of nitrogen in the nitrogen-doped carbon carrier is 1%-30%;
优选地，所述掺氮碳载体的尺寸为100nm～25μm，所述掺氮碳载体的比表面积为200m 2/g～1500m 2/g。 Preferably, the size of the nitrogen-doped carbon support is 100 nm to 25 μm, and the specific surface area of the nitrogen-doped carbon support is 200 m 2 /g to 1500 m 2 /g.
在其中一个实施例中，所述第一次热处理的温度为600℃～800℃，时间为2h～6h；所述第二次热处理的温度为150℃～250℃，时间为1h～8h。In one of the embodiments, the temperature of the first heat treatment is 600°C to 800°C and the time is 2h-6h; the temperature of the second heat treatment is 150°C to 250°C and the time is 1h-8h.
一种燃料电池阴极催化剂，由上述的燃料电池阴极催化剂的制备方法制备得到。A fuel cell cathode catalyst is prepared by the above-mentioned method for preparing a fuel cell cathode catalyst.
还提供一种膜电极，包括上述的燃料电池阴极催化剂。A membrane electrode is also provided, including the above-mentioned fuel cell cathode catalyst.
还提供一种燃料电池，包括上述的膜电极。A fuel cell is also provided, including the above-mentioned membrane electrode.
经试验发现，本发明技术方案的上述燃料电池阴极催化剂的制备方法中， 由于先将碳载体与保护剂混合均匀之后再沉积铂合金纳米颗粒，并依次进行第一次热处理、酸处理以及第二次热处理，得到的燃料电池阴极催化剂中，铂合金纳米颗粒在碳载体上分散均匀，且燃料电池阴极催化剂的催化活性较好，有利于应用。采用上述制备方法制备得到的燃料电池阴极催化剂，催化活性与稳定性俱佳，有利于产业化应用。It is found through experiments that in the preparation method of the above fuel cell cathode catalyst of the technical scheme of the present invention, the platinum alloy nanoparticles are deposited after the carbon support and the protective agent are uniformly mixed, and the first heat treatment, acid treatment and second heat treatment are carried out in sequence. After the second heat treatment, in the fuel cell cathode catalyst obtained, platinum alloy nanoparticles are uniformly dispersed on the carbon support, and the fuel cell cathode catalyst has good catalytic activity, which is favorable for application. The fuel cell cathode catalyst prepared by the above preparation method has excellent catalytic activity and stability, and is beneficial to industrial application.
附图说明Description of the drawings
图1为本发明一实施方式的燃料电池阴极催化剂的制备方法的流程图；Fig. 1 is a flow chart of a method for preparing a fuel cell cathode catalyst according to an embodiment of the present invention;
图2为实施例1制备的燃料电池阴极催化剂的透射电镜(TEM)图；2 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Example 1;
图3为实施例2制备的燃料电池阴极催化剂的透射电镜(TEM)图；Figure 3 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Example 2;
图4为对比例1制备的燃料电池阴极催化剂的透射电镜(TEM)图。4 is a transmission electron microscope (TEM) image of the fuel cell cathode catalyst prepared in Comparative Example 1.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施例的限制。In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the following description, many specific details are explained in order to fully understand the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and/or" as used herein includes any and all combinations of one or more related listed items.
本发明的发明人在研究过程中发现：燃料电池催化剂的性能主要受催化剂的表面结构和组成分布影响，其进步的主要障碍在于难以在纳米层级实现元素分布精确调控。The inventor of the present invention discovered during the research that the performance of the fuel cell catalyst is mainly affected by the surface structure and composition distribution of the catalyst, and the main obstacle to its progress is that it is difficult to achieve precise regulation of element distribution at the nano-level.
为此，本发明提供一种燃料电池阴极催化剂的制备方法，通过提高铂合金纳米颗粒在碳载体上的分散均匀度，来提高燃料电池阴极催化剂的催化活性。To this end, the present invention provides a method for preparing a fuel cell cathode catalyst, which improves the catalytic activity of the fuel cell cathode catalyst by improving the uniformity of the dispersion of platinum alloy nanoparticles on the carbon carrier.
请参见图1，本发明一实施方式的燃料电池阴极催化剂的制备方法，包括如下步骤：Referring to Fig. 1, a method for preparing a fuel cell cathode catalyst according to an embodiment of the present invention includes the following steps:
S10、将碳载体与保护剂的水溶液混合均匀，之后沉积铂合金纳米颗粒，得到沉积有铂合金纳米颗粒的碳载体；其中，铂合金纳米颗粒包括铂和至少一种3d过渡金属。S10. Mix the carbon carrier and the aqueous solution of the protective agent uniformly, and then deposit platinum alloy nanoparticles to obtain a carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles include platinum and at least one 3d transition metal.
步骤S10中，碳载体包括但不限于碳纳米管、碳纳米纤维、介孔碳、碳球或者石墨烯等导电材料。In step S10, the carbon support includes but is not limited to conductive materials such as carbon nanotubes, carbon nanofibers, mesoporous carbon, carbon spheres, or graphene.
步骤S10中，碳载体与保护剂的水溶液混合之后，可以通过搅拌、超声分散等方式实现二者的均匀分散。In step S10, after the aqueous solution of the carbon carrier and the protective agent are mixed, the uniform dispersion of the two can be achieved by means such as stirring, ultrasonic dispersion and the like.
优选地，保护剂为乙酸钠或者十六烷基三甲基溴化铵。经试验证明，这些种类的保护剂能够提高铂合金纳米颗粒在碳载体上的分散均匀度，从而提高燃料电池阴极催化剂的催化活性。Preferably, the protective agent is sodium acetate or cetyltrimethylammonium bromide. Tests have shown that these kinds of protective agents can improve the uniformity of the dispersion of platinum alloy nanoparticles on the carbon support, thereby improving the catalytic activity of the fuel cell cathode catalyst.
更优地，当保护剂为乙酸钠或者十六烷基三甲基溴化铵时，先将保护剂溶解于水中，之后将碳载体加入保护剂的水溶液中混合均匀。经试验证明，这样更有利于能够提高铂合金纳米颗粒在碳载体上的分散均匀度。More preferably, when the protective agent is sodium acetate or cetyltrimethylammonium bromide, the protective agent is first dissolved in water, and then the carbon carrier is added to the aqueous solution of the protective agent and mixed uniformly. Experiments have proved that this is more beneficial to improve the uniformity of the dispersion of platinum alloy nanoparticles on the carbon support.
更优地，沉积铂合金纳米颗粒的操作中，溶液中的金属离子与保护剂的摩尔比为0.05～1.5。经试验证明，上述比例的金属离子与保护剂混合均匀之后，提高了铂合金纳米颗粒在碳载体上的分散均匀度，从而提高燃料电池阴极催化剂的催化活性。More preferably, in the operation of depositing platinum alloy nanoparticles, the molar ratio of the metal ions in the solution to the protective agent is 0.05 to 1.5. Tests have proved that after the metal ions and the protective agent in the above proportion are evenly mixed, the dispersion uniformity of the platinum alloy nanoparticles on the carbon support is improved, thereby improving the catalytic activity of the fuel cell cathode catalyst.
步骤S10中，沉积铂合金纳米颗粒的操作为：将铂前驱体与至少一种3d过渡金属前驱体加入碳载体与保护剂的分散液中，混合均匀，之后加入还原剂，充分反应，即得。其中，加入还原剂的目的是将金属盐还原。还原剂例如可以是硼氢化钠、抗坏血酸或者柠檬酸。In step S10, the operation of depositing platinum alloy nanoparticles is: adding the platinum precursor and at least one 3d transition metal precursor to the dispersion of the carbon carrier and the protective agent, mixing uniformly, and then adding the reducing agent to fully react to obtain . Among them, the purpose of adding the reducing agent is to reduce the metal salt. The reducing agent may be sodium borohydride, ascorbic acid or citric acid, for example.
步骤S10中，3d过渡金属指的是原子的电子排布时最后一个电子排在3d轨道上的金属。例如，钴、镍和铁等金属。In step S10, the 3d transition metal refers to the metal in which the last electron of the atom is arranged on the 3d orbital. For example, metals such as cobalt, nickel, and iron.
优选地，铂合金纳米颗粒包括铂合金核和包裹在铂合金核表面的铂壳。铂壳的厚度为0.5nm～1.5nm。铂合金核占铂合金纳米颗粒的质量分数为40％～75％。Preferably, the platinum alloy nanoparticles include a platinum alloy core and a platinum shell wrapped on the surface of the platinum alloy core. The thickness of the platinum shell is 0.5 nm to 1.5 nm. The platinum alloy core accounts for 40%-75% of the platinum alloy nanoparticles by mass.
优选地，铂合金纳米颗粒选自铂钴合金纳米颗粒、铂镍合金纳米颗粒和铂铁合金纳米颗粒中的至少一种。Preferably, the platinum alloy nanoparticles are selected from at least one of platinum-cobalt alloy nanoparticles, platinum-nickel alloy nanoparticles and platinum-iron alloy nanoparticles.
优选地，铂合金纳米颗粒还包括锰、铱、铑、铌和锆中的一种或两种。Preferably, the platinum alloy nanoparticles further include one or two of manganese, iridium, rhodium, niobium and zirconium.
优选地，铂合金纳米颗粒的粒径范围为3nm～6nm。Preferably, the particle size of platinum alloy nanoparticles ranges from 3 nm to 6 nm.
优选地，铂合金纳米颗粒占燃料电池阴极催化剂的质量分数为30％～50％。Preferably, the mass fraction of platinum alloy nanoparticles in the cathode catalyst of the fuel cell is 30%-50%.
优选地，铂合金纳米颗粒中，铂与3d过渡金属的摩尔比为1:3～5:1。经试验证明，这样有利于提高催化剂的稳定性。Preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to the 3d transition metal is 1:3 to 5:1. Tests have proved that this is beneficial to improve the stability of the catalyst.
S20、对沉积有铂合金纳米颗粒的碳载体依次进行第一次热处理、酸处理以及第二次热处理，得到燃料电池阴极催化剂；其中，第一次热处理的温度为500℃～1000℃，时间为2h～10h；第二次热处理的温度为100℃～300℃，时间为2h～10h。S20. Perform the first heat treatment, acid treatment and second heat treatment on the carbon support deposited with platinum alloy nanoparticles in sequence to obtain a fuel cell cathode catalyst; wherein the temperature of the first heat treatment is 500°C to 1000°C, and the time is 2h～10h; the temperature of the second heat treatment is 100℃～300℃, and the time is 2h～10h.
优选地，对沉积有铂合金纳米颗粒的碳载体进行第一次热处理的操作为：Preferably, the operation of performing the first heat treatment on the carbon support deposited with platinum alloy nanoparticles is:
将沉积有铂合金纳米颗粒的碳载体与含氮化合物混合均匀，之后在惰性气体氛围中500℃～1000℃时热处理2h～10h，得到沉积有铂合金纳米颗粒的掺氮碳载体。The carbon carrier deposited with platinum alloy nanoparticles is uniformly mixed with a nitrogen-containing compound, and then heat-treated in an inert gas atmosphere at 500°C to 1000°C for 2h-10h to obtain a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles.
上述实施方式能够得到负载有铂合金纳米颗粒的掺氮碳载体。掺氮碳载体中，将氮原子引入sp2杂化结构，不仅能大幅改善碳材料的电子特性、表面碱性等物化性质，而且含氮基团可增加碳材料表面吸附金属粒子的活性位，并稳定金属纳米粒子，从而有利于获得高分散性金属负载型催化剂。The above-mentioned embodiment can obtain a nitrogen-doped carbon carrier loaded with platinum alloy nanoparticles. In the nitrogen-doped carbon carrier, the introduction of nitrogen atoms into the sp2 hybrid structure can not only greatly improve the electronic properties, surface alkalinity and other physical and chemical properties of the carbon material, but also the nitrogen-containing groups can increase the active sites of the carbon material surface to adsorb metal particles, and Stabilize the metal nanoparticles, thereby facilitating the acquisition of highly dispersible metal-supported catalysts.
进一步地，将沉积有铂合金纳米颗粒的碳载体与含氮化合物混合均匀的步骤之前，还包括对沉积有铂合金纳米颗粒的碳载体进行酸处理的步骤。目的是对碳载体和铂合金颗粒同时进行活化和消耗3d过渡金属。Further, before the step of uniformly mixing the carbon carrier deposited with platinum alloy nanoparticles and the nitrogen-containing compound, it further includes a step of acid-treating the carbon carrier deposited with platinum alloy nanoparticles. The purpose is to activate the carbon support and platinum alloy particles simultaneously and consume 3d transition metals.
更优地，掺氮碳载体中氮的质量分数为1％～30％；More preferably, the mass fraction of nitrogen in the nitrogen-doped carbon carrier is 1%-30%;
更优地，掺氮碳载体的尺寸为100nm～25μm，掺氮碳载体的比表面积为200m 2/g～1500m 2/g。能够在确保催化剂负载量的前提下优化碳载体的稳定性。 More preferably, the size of the nitrogen-doped carbon support is 100 nm-25 μm, and the specific surface area of the nitrogen-doped carbon support is 200 m 2 /g-1500 m 2 /g. The stability of the carbon support can be optimized under the premise of ensuring the catalyst loading.
步骤S20中，酸处理指的是将沉积有铂合金纳米颗粒的掺氮碳载体浸泡在酸溶液中，维持一段时间之后拿出即可。其中，浸泡的过程中可以加以搅拌处 理。通过酸处理有利于消耗铂合金纳米颗粒表层的3d过渡金属，提高合金催化剂的稳定性。In step S20, acid treatment refers to immersing the nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles in an acid solution, and then taking it out after maintaining it for a period of time. Among them, the process of soaking can be stirred. The acid treatment is beneficial to consume the 3d transition metal on the surface of the platinum alloy nanoparticles and improve the stability of the alloy catalyst.
其中，酸处理过程中用到的酸优选为醋酸、硫酸、硝酸和高氯酸中的至少一种。优选地，酸处理环境的pH小于1，酸处理的温度为50℃～80℃，酸处理的时间为1h～12h。Among them, the acid used in the acid treatment is preferably at least one of acetic acid, sulfuric acid, nitric acid, and perchloric acid. Preferably, the pH of the acid treatment environment is less than 1, the temperature of the acid treatment is 50°C to 80°C, and the time of the acid treatment is 1 hour to 12 hours.
经过步骤S20中的第二次热处理之后，能够降低催化剂的表面缺陷，增加铂在催化剂表层的分布，使其更容易与掺氮的碳载体结合，从而提高稳定性。After the second heat treatment in step S20, the surface defects of the catalyst can be reduced, and the distribution of platinum on the surface of the catalyst can be increased, making it easier to combine with the nitrogen-doped carbon support, thereby improving stability.
第一次热处理和第二次热处理均可以在惰性气体氛围内或者含氧氛围中进行。优选地，第一次热处理的温度为600℃～800℃，时间为2h～6h；第二次热处理的温度为150℃～250℃，时间为1h～8h。通过第一次热处理和第二次热处理在上述温度和时间上的结合，能够使得最终制备得到的燃料电池阴极催化剂的催化活性与稳定性俱佳。Both the first heat treatment and the second heat treatment can be performed in an inert gas atmosphere or an oxygen-containing atmosphere. Preferably, the temperature of the first heat treatment is 600°C to 800°C and the time is 2h-6h; the temperature of the second heat treatment is 150°C to 250°C and the time is 1h-8h. Through the combination of the first heat treatment and the second heat treatment at the above temperature and time, the catalytic activity and stability of the finally prepared fuel cell cathode catalyst can be improved.
经试验发现，本发明技术方案的上述燃料电池阴极催化剂的制备方法中，由于先将碳载体与保护剂混合均匀之后再沉积铂合金纳米颗粒，并依次进行第一次热处理、酸处理以及第二次热处理，得到的燃料电池阴极催化剂中，铂合金纳米颗粒在碳载体上分散均匀，且燃料电池阴极催化剂的催化活性较好，有利于应用。It is found through experiments that in the preparation method of the above fuel cell cathode catalyst of the technical scheme of the present invention, the platinum alloy nanoparticles are deposited after the carbon support and the protective agent are mixed uniformly, and the first heat treatment, acid treatment and second heat treatment are carried out in sequence. After the second heat treatment, in the fuel cell cathode catalyst obtained, platinum alloy nanoparticles are uniformly dispersed on the carbon support, and the fuel cell cathode catalyst has good catalytic activity, which is favorable for application.
一实施方式的燃料电池阴极催化剂，由上述的燃料电池阴极催化剂的制备方法制备得到。The fuel cell cathode catalyst of one embodiment is prepared by the above-mentioned method for preparing the fuel cell cathode catalyst.
采用上述制备方法制备得到的燃料电池阴极催化剂，催化活性与稳定性俱佳，有利于产业化应用。The fuel cell cathode catalyst prepared by the above preparation method has excellent catalytic activity and stability, and is beneficial to industrial application.
一实施方式的膜电极，包括上述的燃料电池阴极催化剂。The membrane electrode of one embodiment includes the above-mentioned fuel cell cathode catalyst.
一实施方式的燃料电池，包括上述的膜电极。The fuel cell of one embodiment includes the above-mentioned membrane electrode.
下面结合具体实施例对本发明的燃料电池阴极催化剂及其制备方法、膜电极及燃料电池进行进一步地说明。In the following, the fuel cell cathode catalyst, the preparation method thereof, the membrane electrode and the fuel cell of the present invention will be further described with reference to specific examples.
实施例1Example 1
向烧瓶中加入40ml水和120mg乙酸钠，超声溶解，称取45mg VcxMax22 碳黑添加到上述溶液中，超声5min并置于搅拌器上持续搅拌60min，然后使用细胞粉碎仪超声分散40min。之后将上述分散液倒入100ml烧杯中并不断搅拌，随后将40mg PtCl 4和28.2mg NiCl 2·6H 2O加入到分散液中，搅拌3h。随后将含有100mg硼氢化钠的水溶液倒入混合液中，搅拌过夜。将完全反应的悬浊液用水离心洗涤，置于60℃真空烘箱过夜，得到干燥后的粉末。 Add 40ml of water and 120mg of sodium acetate to the flask, dissolve by ultrasonic, weigh 45mg of VcxMax22 carbon black and add it to the above solution, sonicate for 5min and place on a stirrer for continuous stirring for 60min, then use a cell pulverizer to ultrasonically disperse for 40min. Then, the above dispersion was poured into a 100 ml beaker and stirred continuously, and then 40 mg PtCl 4 and 28.2 mg NiCl 2 ·6H 2 O were added to the dispersion and stirred for 3 hours. Subsequently, an aqueous solution containing 100 mg of sodium borohydride was poured into the mixed solution and stirred overnight. The completely reacted suspension was washed by centrifugation with water, and placed in a vacuum oven at 60°C overnight to obtain a dried powder.
将干燥后的粉末在400℃下第一次热处理2h，结束后待体系自然冷却。配置10ml浓度为0.5mol/L的硫酸溶液，加入到烧瓶中，置于70℃油浴中酸处理反应24h，待反应结束，用去离子水离心洗涤，最后置于真空干燥箱中干燥。干燥后的粉末置于400℃第二次热处理2h，结束待体系自然冷却，得到实施例1的燃料电池阴极催化剂。The dried powder was heat-treated for the first time at 400°C for 2 hours, and the system was allowed to cool naturally after the end. Prepare 10ml sulfuric acid solution with a concentration of 0.5mol/L, add it to the flask, place it in a 70℃ oil bath for acid treatment for 24h, after the reaction is over, wash with deionized water by centrifugation, and finally place it in a vacuum drying oven to dry. The dried powder was placed at 400° C. for a second heat treatment for 2 hours, and the system was naturally cooled after the end, and the fuel cell cathode catalyst of Example 1 was obtained.
实施例2Example 2
与实施例1的区别在于：保护剂为CTAB(十六烷基三甲基溴化铵)，加入的量为75mg。The difference from Example 1 is that the protective agent is CTAB (hexadecyl trimethyl ammonium bromide), and the added amount is 75 mg.
实施例3Example 3
向烧瓶中加入40ml水和120mg乙酸钠，超声溶解，称取45mg VcxMax22碳黑添加到上述溶液中，超声5min并置于搅拌器上持续搅拌60min，然后使用细胞粉碎仪超声分散40min。之后将上述分散液倒入100ml烧杯中并不断搅拌，随后将40mg PtCl 4和28.2mg NiCl 2·6H 2O加入到分散液中，搅拌3h。随后将含有100mg硼氢化钠的水溶液倒入混合液中，搅拌过夜。将完全反应的悬浊液用水离心洗涤，置于60℃真空烘箱过夜，得到干燥后的粉末。 Add 40ml of water and 120mg of sodium acetate to the flask, dissolve by ultrasonic, weigh 45mg of VcxMax22 carbon black and add it to the above solution, sonicate for 5min and place on a stirrer for continuous stirring for 60min, then use a cell pulverizer to ultrasonically disperse for 40min. Then, the above dispersion was poured into a 100 ml beaker and stirred continuously, and then 40 mg PtCl 4 and 28.2 mg NiCl 2 ·6H 2 O were added to the dispersion and stirred for 3 hours. Subsequently, an aqueous solution containing 100 mg of sodium borohydride was poured into the mixed solution and stirred overnight. The completely reacted suspension was washed by centrifugation with water, and placed in a vacuum oven at 60°C overnight to obtain a dried powder.
将干燥后的粉末在氨气氛围700℃第一次热处理4h，结束后待体系自然冷却。配置10ml浓度为0.5mol/L的硫酸溶液，加入到烧瓶中，置于70℃油浴中酸处理反应2h，待反应结束，用去离子水离心洗涤，最后置于真空干燥箱中干燥。干燥后的粉末置于250℃第二次热处理1h，结束待体系自然冷却，得到实施例3的燃料电池阴极催化剂。The dried powder was heat-treated for the first time at 700°C in an ammonia atmosphere for 4 hours, after which the system was allowed to cool naturally. Prepare 10ml of sulfuric acid solution with a concentration of 0.5mol/L, add it to the flask, and place it in a 70℃ oil bath for acid treatment for 2h. After the reaction is over, wash with deionized water by centrifugation, and finally place it in a vacuum drying oven to dry. The dried powder was placed at 250° C. for a second heat treatment for 1 hour, and the system was left to cool naturally after the end, and the fuel cell cathode catalyst of Example 3 was obtained.
实施例4Example 4
与实施例1的区别在于：第一次热处理的温度为600℃，时间为3h；第二 次热处理的温度为150℃，时间为1h。The difference from Example 1 is that the temperature of the first heat treatment is 600°C and the time is 3 hours; the temperature of the second heat treatment is 150°C and the time is 1 hour.
实施例5：膜电极(MEA)Example 5: Membrane Electrode (MEA)
阴极ink制备：将400mg实施例1制备的燃料电池阴极催化剂加入玻璃瓶，用10g去离子水(Milli-Q)，15mg异丙醇(IPA)，4.5ml 5wt％ Nafion溶液(D520)，混合均匀，得到阴极ink。Cathode ink preparation: Add 400mg of the fuel cell cathode catalyst prepared in Example 1 into a glass bottle, mix well with 10g deionized water (Milli-Q), 15mg isopropanol (IPA), 4.5ml 5wt% Nafion solution (D520) , Get the cathode ink.
阳极ink制备：将Johnson Matthey产的HiSPEC4000型催化剂，采用与上述相似方法，配制成均一的悬浮液。Anode ink preparation: The HiSPEC4000 catalyst produced by Johnson Matthey is prepared into a uniform suspension using a method similar to the above.
MEA制备(CCM模式)：采用超声波喷涂设备(美国USI产，Prism 4000型)，将上述阴极ink与阳极ink分别涂布到质子交换膜(Nafion 212)的两面，催化剂层面积为5cm 2，定量控制Pt载量分别为阳极0.1mg/cm 2，阴极0.4mg/cm 2。 MEA preparation (CCM mode): Using ultrasonic spraying equipment (USI product, Prism 4000 type), the above cathode ink and anode ink are respectively coated on both sides of the proton exchange membrane (Nafion 212), the area of the catalyst layer is 5cm 2 , quantitative controls were anode Pt loading 0.1mg / cm 2, the cathode 0.4mg / cm 2.
实施例6：燃料电池Example 6: Fuel cell
选取5cm 2的实施例7制备得到的两层MEA，贴附的2.5cm 2*2.5cm 2的气体扩散层GDL(SGL 28BC，厚度235μm)，再在两层之间加入180μm厚度垫片，用单电池夹具封装，用4.2N-m加以组装完成单电池。 Choose a 5cm 2 two-layer MEA prepared in Example 7 and attach a 2.5cm 2 *2.5cm 2 gas diffusion layer GDL (SGL 28BC, thickness 235μm), and then add a 180μm thick gasket between the two layers. The single cell clamp is packaged and assembled with 4.2Nm to complete the single cell.
对比例1Comparative example 1
与实施例1的区别在于：不加乙酸钠。The difference from Example 1 is that no sodium acetate is added.
对实施例1、实施例2和对比例1制得的燃料电池阴极催化剂进行扫描电镜表征，分别得到图2、图3和图4。由图2、图3和图4进行对比可以看出，实施例1和实施例2制得的燃料电池阴极催化剂中，铂镍纳米颗粒在碳载体上分散均匀，表明采用本申请的制备方法提高了铂合金纳米颗粒在碳载体上的负载均匀度。The fuel cell cathode catalysts prepared in Example 1, Example 2 and Comparative Example 1 were characterized by scanning electron microscopy, and Figure 2, Figure 3, and Figure 4 were obtained, respectively. From the comparison of Figure 2, Figure 3 and Figure 4, it can be seen that in the fuel cell cathode catalyst prepared in Example 1 and Example 2, platinum nickel nanoparticles are uniformly dispersed on the carbon support, indicating that the preparation method of the present application improves The uniformity of the platinum alloy nanoparticles on the carbon support is described.
对实施例1、实施例2和对比例1的燃料电池阴极催化剂分别进行电化学表面积、比活性、质量活性与稳定性测试。测试过程如下：The fuel cell cathode catalysts of Example 1, Example 2 and Comparative Example 1 were tested for electrochemical surface area, specific activity, mass activity and stability respectively. The test process is as follows:
组装旋转圆盘电极(Rotating Disk Electrode，RDE)进行测试，取实施例和对比例配制好的催化剂墨水滴涂在工作电极上，CV测试条件是电解质为N 2饱和的0.1M HClO4水溶液，相对于可逆氢电极电势范围为0.05V～1.1V，扫描速度为100mV/s；氧还原测试条件为电解质为O 2饱和的0.1M HClO 4水溶液，相对 于可逆氢电极电势范围为0.05V～1.1V，扫描速度为20mV/s。 Assembly rotating disk electrode (Rotating Disk Electrode, RDE) test, and Comparative Example taken formulated catalyst ink is dispensed onto the working electrode, the CV test conditions 0.1M HClO4 electrolyte of a saturated aqueous solution of N 2, with respect to The potential range of the reversible hydrogen electrode is 0.05V～1.1V, and the scanning speed is 100mV/s; the oxygen reduction test condition is that the electrolyte is a 0.1M HClO 4 aqueous solution saturated with O 2 and the potential range of the reversible hydrogen electrode is 0.05V～1.1V. The scanning speed is 20mV/s.
测试结果如表1所示：The test results are shown in Table 1:
表1实施例1、实施例2和对比例1的燃料电池阴极催化剂的测试数据Table 1 Test data of the fuel cell cathode catalysts of Example 1, Example 2 and Comparative Example 1
Figure PCTCN2019124139-appb-000001
Figure PCTCN2019124139-appb-000001
从表1可以看出，与对比例1～2的燃料电池阴极催化剂相比，实施例1和实施例2的燃料电池阴极催化剂的电化学表面积、比活性、质量活性和稳定性均较高，表明实施例1和实施例2的燃料电池阴极催化剂中，负载在碳载体表面的铂合金纳米颗粒更稳定，排列更规整，从而使得催化活性与稳定性俱佳。As can be seen from Table 1, compared with the fuel cell cathode catalysts of Comparative Examples 1 to 2, the fuel cell cathode catalysts of Example 1 and Example 2 have higher electrochemical surface area, specific activity, mass activity and stability. It shows that in the fuel cell cathode catalysts of Example 1 and Example 2, the platinum alloy nanoparticles supported on the surface of the carbon support are more stable and arranged more regular, so that the catalytic activity and stability are both better.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their description is relatively specific and detailed, but they should not be understood as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种燃料电池阴极催化剂的制备方法，其特征在于，包括如下步骤：A preparation method of a fuel cell cathode catalyst is characterized in that it comprises the following steps:
    将碳载体与保护剂的水溶液混合均匀，之后沉积铂合金纳米颗粒，得到沉积有铂合金纳米颗粒的碳载体；其中，所述铂合金纳米颗粒包括铂和至少一种3d过渡金属；以及The carbon carrier and the aqueous solution of the protective agent are uniformly mixed, and then platinum alloy nanoparticles are deposited to obtain a carbon carrier deposited with platinum alloy nanoparticles; wherein the platinum alloy nanoparticles include platinum and at least one 3d transition metal; and
    对所述沉积有铂合金纳米颗粒的碳载体依次进行第一次热处理、酸处理以及第二次热处理，得到燃料电池阴极催化剂；Performing a first heat treatment, an acid treatment and a second heat treatment on the carbon support deposited with platinum alloy nanoparticles in sequence to obtain a fuel cell cathode catalyst;
    其中，第一次热处理的温度为500℃～1000℃，时间为2h～10h；第二次热处理的温度为100℃～300℃，时间为2h～10h。Among them, the temperature of the first heat treatment is 500°C to 1000°C, and the time is 2h-10h; the temperature of the second heat treatment is 100°C to 300°C, and the time is 2h-10h.
  2. 根据权利要求1所述的燃料电池阴极催化剂的制备方法，其特征在于，所述保护剂为乙酸钠或者十六烷基三甲基溴化铵。The method for preparing a fuel cell cathode catalyst according to claim 1, wherein the protective agent is sodium acetate or cetyltrimethylammonium bromide.
  3. 根据权利要求1或2所述的燃料电池阴极催化剂的制备方法，其特征在于，沉积铂合金纳米颗粒的操作中，溶液中的金属离子与所述保护剂的摩尔比为0.05～1.5。The method for preparing a fuel cell cathode catalyst according to claim 1 or 2, wherein in the operation of depositing platinum alloy nanoparticles, the molar ratio of metal ions in the solution to the protective agent is 0.05 to 1.5.
  4. 根据权利要求1所述的燃料电池阴极催化剂的制备方法，其特征在于，所述铂合金纳米颗粒包括铂合金核和包裹在所述铂合金核表面的铂壳；The method for preparing a fuel cell cathode catalyst according to claim 1, wherein the platinum alloy nanoparticles comprise a platinum alloy core and a platinum shell wrapped on the surface of the platinum alloy core;
    所述铂壳的厚度为0.5nm～1.5nm；The thickness of the platinum shell is 0.5 nm to 1.5 nm;
    所述铂合金核占所述铂合金纳米颗粒的质量分数为40％～75％；The platinum alloy core accounts for 40% to 75% of the platinum alloy nanoparticles by mass;
    优选地，铂合金纳米颗粒选自铂钴合金纳米颗粒、铂镍合金纳米颗粒和铂铁合金纳米颗粒中的至少一种；Preferably, the platinum alloy nanoparticles are selected from at least one of platinum-cobalt alloy nanoparticles, platinum-nickel alloy nanoparticles and platinum-iron alloy nanoparticles;
    优选地，所述铂合金纳米颗粒占所述燃料电池阴极催化剂的质量分数为30％～50％；Preferably, the mass fraction of the platinum alloy nanoparticles in the cathode catalyst of the fuel cell is 30%-50%;
    优选地，所述铂合金纳米颗粒中，铂与3d过渡金属的摩尔比为1:3～5:1。Preferably, in the platinum alloy nanoparticles, the molar ratio of platinum to 3d transition metal is 1:3 to 5:1.
  5. 根据权利要求1所述的燃料电池阴极催化剂的制备方法，其特征在于，对所述沉积有铂合金纳米颗粒的碳载体进行第一次热处理的操作为：The method for preparing a fuel cell cathode catalyst according to claim 1, wherein the operation of performing the first heat treatment on the carbon support deposited with platinum alloy nanoparticles is:
    将所述沉积有铂合金纳米颗粒的碳载体与含氮化合物混合均匀，之后在惰 性气体氛围中400℃～1000℃时热处理2h～10h，得到沉积有铂合金纳米颗粒的掺氮碳载体。The carbon carrier deposited with platinum alloy nanoparticles is uniformly mixed with a nitrogen-containing compound, and then heat-treated in an inert gas atmosphere at 400°C to 1000°C for 2h-10h to obtain a nitrogen-doped carbon carrier deposited with platinum alloy nanoparticles.
  6. 根据权利要求5所述的燃料电池阴极催化剂的制备方法，其特征在于，所述掺氮碳载体中氮的质量分数为1％～30％；The method for preparing a fuel cell cathode catalyst according to claim 5, wherein the mass fraction of nitrogen in the nitrogen-doped carbon support is 1%-30%;
    优选地，所述掺氮碳载体的尺寸为100nm～25μm，所述掺氮碳载体的比表面积为200m 2/g～1500m 2/g。 Preferably, the size of the nitrogen-doped carbon support is 100 nm to 25 μm, and the specific surface area of the nitrogen-doped carbon support is 200 m 2 /g to 1500 m 2 /g.
  7. 根据权利要求1中任一项所述的燃料电池阴极催化剂的制备方法，其特征在于，所述第一次热处理的温度为600℃～800℃，时间为2h～6h；所述第二次热处理的温度为150℃～250℃，时间为1h～8h。The method for preparing a fuel cell cathode catalyst according to any one of claims 1, wherein the temperature of the first heat treatment is 600°C to 800°C, and the time is 2h to 6h; the second heat treatment The temperature is 150℃～250℃, and the time is 1h～8h.
  8. 一种燃料电池阴极催化剂，其特征在于，由权利要求1～7中任一项所述的燃料电池阴极催化剂的制备方法制备得到。A fuel cell cathode catalyst characterized by being prepared by the method for preparing a fuel cell cathode catalyst according to any one of claims 1-7.
  9. 一种膜电极，其特征在于，包括权利要求8所述的燃料电池阴极催化剂。A membrane electrode, characterized by comprising the fuel cell cathode catalyst of claim 8.
  10. 一种燃料电池，其特征在于，包括权利要求9所述的膜电极。A fuel cell, characterized by comprising the membrane electrode according to claim 9.
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