WO2020042535A1 - Conductive corrosion-resistant coating for metal bipolar plate of fuel cell - Google Patents

Conductive corrosion-resistant coating for metal bipolar plate of fuel cell Download PDF

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WO2020042535A1
WO2020042535A1 PCT/CN2019/072824 CN2019072824W WO2020042535A1 WO 2020042535 A1 WO2020042535 A1 WO 2020042535A1 CN 2019072824 W CN2019072824 W CN 2019072824W WO 2020042535 A1 WO2020042535 A1 WO 2020042535A1
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coating
metal
bipolar plate
corrosion
fuel cell
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PCT/CN2019/072824
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French (fr)
Chinese (zh)
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易培云
邱殿凯
姚力
樊帆
李骁博
彭林法
来新民
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上海交通大学
上海汽车集团股份有限公司
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Publication of WO2020042535A1 publication Critical patent/WO2020042535A1/en

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • 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 belongs to the technical field of fuel cells and relates to a low-cost doping method for a fuel cell metal bipolar plate conductive corrosion-resistant coating.
  • Fuel cells use hydrogen as an energy source, which has many advantages such as high efficiency and environmental protection, high specific energy and specific power, and fast startup. It has a wide range of applications in various fields.
  • the bipolar plate as one of the key components of the fuel cell, has the key functions of supporting the structure of the cell, distributing the reaction gas, collecting current, and connecting the cells in series. Therefore, its performance restricts the commercialization process of the fuel cell.
  • graphite or metal is commonly used as the material of bipolar plates.
  • graphite bipolar plates have the disadvantages of difficulty in processing, gas permeation, and poor mechanical properties.
  • Metal bipolar plates have good mechanical properties, ease of processing, and Gas permeation, low cost and other advantages have become the main materials of fuel cell bipolar plates.
  • Fuel cell metal bipolar plates generally work in a high-temperature, high-humidity, acidic environment with a pH of 2-5 and a temperature of 70-100 ° C.
  • metal bipolar plates in service in this environment is usually passivated to form a dense, dense,
  • the poorly conductive metal oxide film causes the contact resistance between the metal plate and the gas diffusion layer to increase, which in turn leads to an increase in the voltage loss of the battery due to ohmic polarization and a decrease in battery output power.
  • metal ions in the bipolar plate are released due to corrosion. It also reacts with the catalyst and membrane electrode, which affects the reaction activity and mass transfer of the battery, and further affects the battery performance. Therefore, metal bipolar plates alone cannot meet the requirements for the use of fuel cells.
  • functional thin films can be plated on the surface of metal bipolar plates by methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), ion plating, chemical plating, and electroplating to improve their corrosion resistance and conductivity.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • ion plating chemical plating
  • electroplating to improve their corrosion resistance and conductivity.
  • Commonly used functional films include amorphous carbon films, metal carbide films, metal nitride films, precious metal films, organic films, etc.
  • precious metal films have good conductivity, corrosion resistance and stability, but their cost is difficult
  • commercial applications while non-precious metal coatings have lower production costs, but their performance is inferior to that of precious metals, and currently cannot meet the fuel cell life requirements.
  • the object of the present invention can be achieved by the following technical scheme: a conductive corrosion-resistant coating for a fuel cell metal bipolar plate, characterized in that the coating is composed of a precious metal part and a conductive and corrosion-resistant non-precious metal part, wherein the precious metal is The proportion in the coating is 10-90 wt%.
  • Precious metal part used to ensure better conductivity, corrosion resistance and stability of metal bipolar plates;
  • Non-precious metal part Used to reduce the amount of precious metal in the coating under the premise of ensuring the performance of the metal bipolar plate, thereby reducing the coating cost.
  • Non-noble metals can be doped with precious metals in different forms.
  • Specific doping methods include the following three:
  • the non-noble metal part is randomly embedded in the noble metal part as a filler to form a coating.
  • the non-precious metal part is randomly and uniformly embedded in the precious metal part to form a mixed coating of precious metal and non-precious metal, and the thickness of the mixed coating does not exceed 200 nm.
  • the non-noble metal part and the precious metal part are alternately arranged on the surface of the bipolar plate to form a multilayer coating structure, and the outermost layer of the coating is the surface of the noble metal to ensure the better conductivity, corrosion resistance and Stability, the thickness of each layer of precious metal coating or non-precious metal coating is 1-20nm, and the total thickness of the coating does not exceed 200nm.
  • the coating is formed by plating a precious metal coating on a contact portion of the metal bipolar plate with a flow channel and a gas diffusion layer, and plating a non-precious metal coating on a non-contact portion.
  • a mask is required to control the coating deposition at different positions. After the deposition of the precious metal coating is finished, the mask can be processed to recover the precious metal and reduce the precious metal in the coating. At the same time, the remaining precious metal is recycled to further reduce the cost of the coating. On the premise of ensuring the performance of the coating, the proportion of the precious metal in the coating is further reduced to 10-30%, which can further reduce the cost of coating preparation;
  • the non-noble metal portion includes a metal element or a non-metal element, or a metal compound.
  • the metal element includes Ti, Cr, W, Zr, Nb, Ta or Mo
  • the non-metal element includes C, N, H or O
  • the metal compound is composed of the foregoing metal element and non-metal element. Metal compounds.
  • the proportion of the non-noble metal portion in the coating is 10-90 wt%.
  • the conductive and corrosion-resistant coating is prepared by a single-chamber magnetron sputtering coating equipment, or a continuous magnetron sputtering coating equipment.
  • the thickness of the conductive corrosion-resistant coating is 10-200 nm.
  • the magnetron sputtering can be prepared in batches by using a single-chamber multi-furnace magnetron sputtering device;
  • magnetron sputtering can also be used for batch preparation of coatings by continuous magnetron coating equipment;
  • the coating deposited on the surface of the metal bipolar plate in order to further improve the corrosion resistance of the coating and improve the adhesion of the film base, a layer of a corrosion-resistant metal substrate can be deposited on the surface of the metal bipolar plate in advance, and Pre-deposited precious metal coating on the metal bottom;
  • the corrosion-resistant metal underlayer mainly includes one or more of Ti, Cr, W, Zr, Nb, Ta, etc .;
  • the total thickness of the coating is 10-300 nm.
  • the method for preparing a low-cost, highly conductive, and corrosion-resistant precious metal coating for a fuel cell metal bipolar plate includes the following steps:
  • the surface of the metal bipolar plate is plated with a corrosion-resistant metal substrate
  • the conductive anticorrosive coating is deposited on the surface of the metal base layer according to different doping methods.
  • the low-cost non-precious metal portion is incorporated into the high-performance precious metal coating by different methods. Compared with the prior art, the present invention has the following advantages:
  • the coating still has the excellent physical and chemical properties of the precious metal coating, which can ensure that the fuel cell metal bipolar plate has high conductivity, corrosion resistance and stability during service;
  • the invention is of great significance for improving the performance of fuel cell metal bipolar plates and advancing the industrialization process of fuel cells.
  • FIG. 1 is a schematic diagram of the overall structure of the coating prepared in Examples 1 and 2;
  • Example 2 is a schematic diagram of the overall structure of the coating prepared in Example 3.
  • Example 3 is a schematic diagram of the overall structure of the coating prepared in Example 5;
  • FIG. 4 is a graph of measurement results of contact resistance of the coatings prepared in Examples 1-5 and a pure gold thin film
  • 1 metal bipolar plate
  • 2 corrosion-resistant non-precious metal layer
  • 3 precious metal layer
  • 4 non-precious metal filler
  • 5 gas diffusion layer
  • a method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
  • the second layer of the anti-corrosive metal deposited in the second step was sputtered together with the Au target and the Ti target by magnetron sputtering, and the precious metal 3 and non-noble metal 4 components in the coating were adjusted by controlling the process parameters. Control the process time to ensure that the thickness of the deposited coating is 50nm;
  • FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
  • the initial contact resistance of the coating prepared in this example is 1.52 m ⁇ ⁇ cm 2 , and the conductivity is basically unchanged.
  • PH 3 , 80 ° C H 2 SO 4 (containing 0.1 (ppm HF) solution 1.60V (vs SHE) constant potential polarization 1h corrosion current density is stable at 6.6E-7A / cm 2 , corrosion resistance is improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
  • a method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
  • the second layer of the anti-corrosive metal deposited in the second step was sputtered on the Au target by magnetron sputtering, while TiC was deposited by reactive sputtering, and the precious metals in the coating were controlled by the control of process parameters. Proportion to 4 components of non-precious metal, control the process time to ensure the thickness of the deposited coating is 100nm;
  • FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
  • the initial contact resistance of the coating prepared in this example is 1.64 m ⁇ ⁇ cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged.
  • ppm HF ppm HF
  • 1h corrosion current density is stable at 8.5E-7A / cm 2 , corrosion resistance is improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
  • a method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
  • a 20 nm corrosion-resistant metal Cr is deposited on the base layer 2 in advance to improve the corrosion resistance of the coating and improve the adhesion of the film base;
  • step 2 on the surface where the coating is deposited in the third step;
  • step 3 Repeat step 3 on the surface where the coating is deposited in the fourth step;
  • FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
  • the initial contact resistance of the coating prepared in this example is 1.66 m ⁇ ⁇ cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged.
  • the pH is 3 at 80 ° C and H 2 SO 4 (containing 0.1).
  • the corrosion current density in the 1.60V (vs SHE) constant potential polarization for 1h in the solution of ppm (HF) was stable at 1.3E-7A / cm 2 , and the corrosion resistance was significantly improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
  • a method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
  • a 20 nm corrosion-resistant metal Cr is deposited on the base layer 2 in advance to improve the corrosion resistance of the coating and improve the adhesion of the film base;
  • step 3 Repeat step 3 on the surface where the coating is deposited in the fourth step;
  • step 4 on the surface where the coating is deposited in the fourth step;
  • step 3 Repeat step 3 on the surface where the coating is deposited in the fourth step;
  • step 4 on the surface where the coating is deposited in the fourth step;
  • FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
  • the initial contact resistance of the coating prepared in this example is 1.86 m ⁇ ⁇ cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged.
  • the corrosion current density is stable at 5.8E-7A / cm 2 at 1.60V (vs SHE) constant potential polarization for 1h in the solution of ppm HF), and the corrosion resistance is slightly improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
  • a method for preparing a low-cost, highly conductive, and corrosion-resistant precious metal coating for a fuel cell metal bipolar plate includes the following steps:
  • a 30 nm layer of corrosion-resistant metal Ti is deposited on all surfaces of the metal bipolar plate 1 after the first treatment to improve the corrosion resistance of the coating;
  • FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
  • the initial contact resistance of the coating prepared in this example is 1.98 m ⁇ ⁇ cm 2 compared to a pure gold thin film, and the conductivity is slightly reduced.
  • the pH is 3 at 80 ° C for H 2 SO 4 (containing 0.1).
  • the corrosion current density is stable at 1.5E-6A / cm 2 at 1.60V (vs SHE) constant potential polarization in a solution of 1.60V (vs SHE) in a ppm HF) solution, but the corrosion resistance slightly decreases, but the coating still has superior performance. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.

Abstract

The invention relates to a conductive corrosion-resistant coating for a metal bipolar plate of a fuel cell. The coating is composed of a precious metal portion and a conductive, corrosion-resistant non-noble metal portion, in which the precious metal accounts for 10-90 wt% in the coating. The corrosion-resistant non-precious metal material portion is doped into the precious metal coating in different ways. The precious metal in the coating is used to ensure better conductivity, corrosion resistance and stability of the metal bipolar plate. While ensuring the performance of the coating, the anti-corrosive non-precious metal doped therein reduces the amount of precious metal in the coating, thereby reducing coating costs. Compared with the prior art, the present invention adopts a different doping method, which can take advantage of the excellent physical and chemical properties of precious metal to ensure superior performance of the metal bipolar plate and greatly reduce the cost of coating. The invention is of great significance for promoting the industrialization process of fuel cells.

Description

一种燃料电池金属双极板用导电耐蚀涂层Conductive corrosion-resistant coating for metal bipolar plate of fuel cell 技术领域Technical field
本发明属于燃料电池技术领域，涉及用于燃料电池金属双极板导电耐蚀涂层的低成本掺杂方法。The invention belongs to the technical field of fuel cells and relates to a low-cost doping method for a fuel cell metal bipolar plate conductive corrosion-resistant coating.
背景技术Background technique
燃料电池使用氢气作为能源，具有高效环保、比能量和比功率高、启动快等诸多有点，在各个领域具有广泛的应用前景。其中双极板作为燃料电池的关键部件之一，具有支撑电池结构、分配反应气体、收集电流、串联各电池等关键作用，因此其性能好坏制约着燃料电池的商业化进程。Fuel cells use hydrogen as an energy source, which has many advantages such as high efficiency and environmental protection, high specific energy and specific power, and fast startup. It has a wide range of applications in various fields. Among them, the bipolar plate, as one of the key components of the fuel cell, has the key functions of supporting the structure of the cell, distributing the reaction gas, collecting current, and connecting the cells in series. Therefore, its performance restricts the commercialization process of the fuel cell.
目前双极板常用的材料为石墨或金属，其中石墨双极板具有难加工、存在气体渗透、机械性能较差等缺点，而金属双极板因其较好的机械性能、易加工性、无气体渗透、低成本等优点已成为燃料电池双极板主要材料。燃料电池金属双极板一般工作在pH值为2-5、温度为70-100℃的高温高湿酸性环境中，该环境下服役的金属双极板表面通常会发生钝化形成一层致密、导电性差的金属氧化膜，导致金属极板与气体扩散层间接触电阻增大，进而导致电池因欧姆极化产生的电压损失增加，电池输出功率下降，同时双极板中的金属离子因腐蚀释放并与催化剂、膜电极反应，影响电池反应活性及传质，进一步影响电池性能。因此仅靠金属双极板并不能满足燃料电池的使用要求。At present, graphite or metal is commonly used as the material of bipolar plates. Among them, graphite bipolar plates have the disadvantages of difficulty in processing, gas permeation, and poor mechanical properties. Metal bipolar plates have good mechanical properties, ease of processing, and Gas permeation, low cost and other advantages have become the main materials of fuel cell bipolar plates. Fuel cell metal bipolar plates generally work in a high-temperature, high-humidity, acidic environment with a pH of 2-5 and a temperature of 70-100 ° C. The surface of metal bipolar plates in service in this environment is usually passivated to form a dense, dense, The poorly conductive metal oxide film causes the contact resistance between the metal plate and the gas diffusion layer to increase, which in turn leads to an increase in the voltage loss of the battery due to ohmic polarization and a decrease in battery output power. At the same time, metal ions in the bipolar plate are released due to corrosion. It also reacts with the catalyst and membrane electrode, which affects the reaction activity and mass transfer of the battery, and further affects the battery performance. Therefore, metal bipolar plates alone cannot meet the requirements for the use of fuel cells.
目前可通过物理气相沉积(PVD)、化学气相沉积(CVD)、离子镀、化学镀、电镀等方法在金属双极板表面镀覆功能性薄膜，以提高其耐腐蚀性及导电性。常用功能性薄膜包括非晶碳薄膜、金属碳化物薄膜、金属氮化物薄膜、贵金属薄膜、有机物薄膜等，其中贵金属薄膜具备较好的导电性、耐蚀性及稳定性，但其成本较高难以商业化应用，而非贵金属涂层虽制备成本较低，但其性能较贵金属差，目前尚不能满足燃料电池寿命要求。中国专利CN 103484910 A公开了一种采用电镀方法制备的金涂层，随后对金涂层进行热处理以减少涂层孔隙率，但该涂层接触电阻为15-22mΩ·cm 2，电池输出电压将因较高的接触电阻值降低，同时涂层制备成本较高；中国专利CN 101640276 A公开了一种燃 料电池双极板无定型碳涂层，该涂层具备较好的导电性及耐腐蚀性，但数据表明其接触电阻在双极板工作压力下大于10mΩ·cm 2，同时该涂层在长时间电化学测试后导电性能未知。本发明将在保证金属双极板导电耐蚀性能的前提下，通过多种低成本掺杂方法制备燃料电池金属双极板涂层。 Currently, functional thin films can be plated on the surface of metal bipolar plates by methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), ion plating, chemical plating, and electroplating to improve their corrosion resistance and conductivity. Commonly used functional films include amorphous carbon films, metal carbide films, metal nitride films, precious metal films, organic films, etc. Among them, precious metal films have good conductivity, corrosion resistance and stability, but their cost is difficult Commercial applications, while non-precious metal coatings have lower production costs, but their performance is inferior to that of precious metals, and currently cannot meet the fuel cell life requirements. Chinese patent CN 103484910 A discloses a gold coating prepared by electroplating, followed by heat treatment of the gold coating to reduce the porosity of the coating, but the coating has a contact resistance of 15-22 mΩ · cm 2 and the battery output voltage will be Due to the lower contact resistance value and the higher cost of coating preparation; Chinese patent CN 101640276 A discloses an amorphous carbon coating for a fuel cell bipolar plate, which has better conductivity and corrosion resistance However, the data show that its contact resistance is greater than 10mΩ · cm 2 under the working pressure of the bipolar plate, and the conductivity of the coating is unknown after a long-term electrochemical test. The invention will prepare a fuel cell metal bipolar plate coating through a variety of low-cost doping methods on the premise of ensuring the conductivity and corrosion resistance of the metal bipolar plate.
发明内容Summary of the Invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种导电耐蚀性能好且成本低的燃料电池金属双极板用导电耐蚀涂层。The purpose of the present invention is to provide a conductive corrosion-resistant coating for a fuel cell metal bipolar plate with good conductive corrosion resistance and low cost in order to overcome the defects existing in the prior art.
本发明的目的可以通过以下技术方案来实现：一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，该涂层由贵金属部分及导电耐蚀的非贵金属部分组成，其中贵金属在涂层中所占比例为10-90wt％。The object of the present invention can be achieved by the following technical scheme: a conductive corrosion-resistant coating for a fuel cell metal bipolar plate, characterized in that the coating is composed of a precious metal part and a conductive and corrosion-resistant non-precious metal part, wherein the precious metal is The proportion in the coating is 10-90 wt%.
贵金属部分：用以保证金属双极板较好的导电性、耐腐蚀性及稳定性；Precious metal part: used to ensure better conductivity, corrosion resistance and stability of metal bipolar plates;
非贵金属部分：用以在保证金属双极板性能的前提下，降低涂层中贵金属用量，从而降低涂层成本。Non-precious metal part: Used to reduce the amount of precious metal in the coating under the premise of ensuring the performance of the metal bipolar plate, thereby reducing the coating cost.
非贵金属可以不同的形式掺入贵金属，具体掺杂方式包括以下三种：Non-noble metals can be doped with precious metals in different forms. Specific doping methods include the following three:
一、所述的非贵金属部分作为填充物随机嵌入贵金属部分形成涂层。将非贵金属部分随机、均匀地嵌入贵金属部分，形成贵金属与非贵金属混合涂层，混合涂层厚度不超过200nm。1. The non-noble metal part is randomly embedded in the noble metal part as a filler to form a coating. The non-precious metal part is randomly and uniformly embedded in the precious metal part to form a mixed coating of precious metal and non-precious metal, and the thickness of the mixed coating does not exceed 200 nm.
二、所述的非贵金属部分与贵金属部分交替布置在双极板表面形成多层涂层结构，涂层最外层为贵金属表面，以保证金属双极板较好的导电性、耐蚀性及稳定性，每一层贵金属涂层或非贵金属涂层厚度为1-20nm，涂层总厚度不超过200nm。2. The non-noble metal part and the precious metal part are alternately arranged on the surface of the bipolar plate to form a multilayer coating structure, and the outermost layer of the coating is the surface of the noble metal to ensure the better conductivity, corrosion resistance and Stability, the thickness of each layer of precious metal coating or non-precious metal coating is 1-20nm, and the total thickness of the coating does not exceed 200nm.
三、除最外层贵金属涂层外，在保证涂层内部可形成较好的电子传导通路前提下，其余贵金属涂层厚度可尽可能小于非贵金属涂层厚度，以进一步减小贵金属涂层用量，从而降低涂层成本；3. Except for the outermost precious metal coating, on the premise of ensuring that a good electronic conduction path can be formed inside the coating, the thickness of the remaining precious metal coatings can be as small as possible for non-precious metal coatings to further reduce the amount of precious metal coatings. To reduce coating costs;
优选的，所述的涂层由在带有流道的金属双极板与气体扩散层接触部位镀覆贵金属涂层，在非接触部位镀覆非贵金属涂层构成。Preferably, the coating is formed by plating a precious metal coating on a contact portion of the metal bipolar plate with a flow channel and a gas diffusion layer, and plating a non-precious metal coating on a non-contact portion.
进一步地，在对金属双极板镀覆涂层时，需要设置掩膜以控制不同位置的涂层沉积，贵金属涂层沉积结束后可对掩膜进行处理以回收贵金属，在降低涂 层中贵金属用量的同时将剩余贵金属回收利用，以进一步降低涂层成本；，在保证涂层性能的前提下，涂层中贵金属部分占比进一步降低，为10-30％，可进一步缩减涂层制备成本；Further, when coating a metal bipolar plate, a mask is required to control the coating deposition at different positions. After the deposition of the precious metal coating is finished, the mask can be processed to recover the precious metal and reduce the precious metal in the coating. At the same time, the remaining precious metal is recycled to further reduce the cost of the coating. On the premise of ensuring the performance of the coating, the proportion of the precious metal in the coating is further reduced to 10-30%, which can further reduce the cost of coating preparation;
所述的贵金属部分包括Au、Ag、Ru、Rh、Pd、Os、Ir或Pt。The noble metal part includes Au, Ag, Ru, Rh, Pd, Os, Ir or Pt.
所述的非贵金属部分包括金属单质或非金属单质，或金属化合物。The non-noble metal portion includes a metal element or a non-metal element, or a metal compound.
所述的金属单质包括Ti、Cr、W、Zr、Nb、Ta或Mo，所述的非金属单质包括C、N、H或O，所述的金属化合物为前述金属单质和非金属单质组成的金属化合物。The metal element includes Ti, Cr, W, Zr, Nb, Ta or Mo, the non-metal element includes C, N, H or O, and the metal compound is composed of the foregoing metal element and non-metal element. Metal compounds.
进一步地，所述的化合物为导电耐蚀化合物，包括贵金属元素与贵金属形成的化合物，如Au xTi y、Au xNb y、Au xZr y、Pt xTi y、Pt xNb y、Pt xZr y等，亦可包括金属元素与非贵金属元素形成的化合物，如Ti xN y、Ti xC y、Cr xN y、Cr xC y、Zr xC y、Nb xC y、W xC y等。 Further, the compound is a conductive and corrosion-resistant compound, including a compound formed by a noble metal element and a noble metal, such as Au x Ti y , Au x Nb y , Au x Zr y , Pt x Ti y , Pt x Nb y , Pt x Zr y, etc. may also include compounds formed by metal elements and non-noble metal elements, such as Ti x N y , Ti x C y , Cr x N y , Cr x C y , Zr x C y , Nb x C y , W x C y and so on.
所述的非贵金属部分在涂层中所占的比例为10-90wt％。The proportion of the non-noble metal portion in the coating is 10-90 wt%.
所述的导电耐蚀涂层通过单腔体磁控溅射镀膜设备制备，或通过连续式磁控溅射镀膜设备制备。The conductive and corrosion-resistant coating is prepared by a single-chamber magnetron sputtering coating equipment, or a continuous magnetron sputtering coating equipment.
所述的导电耐蚀涂层的厚度为10-200nm。The thickness of the conductive corrosion-resistant coating is 10-200 nm.
优选的，所述的导电耐蚀涂层，可通过磁控溅射的方法制备；Preferably, the conductive and corrosion-resistant coating can be prepared by a magnetron sputtering method;
进一步地，所述的磁控溅射，可采用单腔体多装炉量磁控溅射设备进行涂层批量化制备；Further, the magnetron sputtering can be prepared in batches by using a single-chamber multi-furnace magnetron sputtering device;
进一步地，所述的磁控溅射，亦可通过连续式磁控镀膜设备实现涂层批量化制备；Further, the magnetron sputtering can also be used for batch preparation of coatings by continuous magnetron coating equipment;
优选的，沉积在金属双极板表面的涂层，为进一步提高涂层耐腐蚀性能，同时提高膜基结合力，可预先在金属双极板表面沉积一层耐腐蚀金属底层，而后在耐蚀金属底层再沉积贵金属涂层；Preferably, the coating deposited on the surface of the metal bipolar plate, in order to further improve the corrosion resistance of the coating and improve the adhesion of the film base, a layer of a corrosion-resistant metal substrate can be deposited on the surface of the metal bipolar plate in advance, and Pre-deposited precious metal coating on the metal bottom;
进一步地，所述的耐蚀金属底层，主要包括Ti、Cr、W、Zr、Nb、Ta等中的一种或更多种；Further, the corrosion-resistant metal underlayer mainly includes one or more of Ti, Cr, W, Zr, Nb, Ta, etc .;
进一步地，所述的耐蚀金属底层厚度为1-200nm。Further, the thickness of the bottom layer of the corrosion-resistant metal is 1-200 nm.
优选的，所述的涂层总厚度为10-300nm。Preferably, the total thickness of the coating is 10-300 nm.
上述用于燃料电池金属双极板的低成本、高导电、耐腐蚀贵金属涂层的制 备方法，包括以下步骤：The method for preparing a low-cost, highly conductive, and corrosion-resistant precious metal coating for a fuel cell metal bipolar plate includes the following steps:
1)清洗金属双极板表面以去除其表面油污及氧化膜；1) Clean the surface of the metal bipolar plate to remove the surface oil and oxide film;
2)在金属双极板表面镀覆耐蚀金属打底层；2) The surface of the metal bipolar plate is plated with a corrosion-resistant metal substrate;
3)在金属打底层表面按不同掺杂方法沉积导电耐蚀涂层。3) The conductive anticorrosive coating is deposited on the surface of the metal base layer according to different doping methods.
本发明中，通过在不同方法将低成本的非贵金属部分掺入高性能的贵金属涂层中，与现有技术相比，本发明具有以下优点：In the present invention, the low-cost non-precious metal portion is incorporated into the high-performance precious metal coating by different methods. Compared with the prior art, the present invention has the following advantages:
1)涂层依旧具有贵金属涂层优良的物理、化学特性，可保证燃料电池金属双极板在服役过程中具有较高的导电性、耐腐蚀性及稳定性；1) The coating still has the excellent physical and chemical properties of the precious metal coating, which can ensure that the fuel cell metal bipolar plate has high conductivity, corrosion resistance and stability during service;
2)涂层中贵金属用量明显减少，同时非贵金属涂层制备方法简单，因此涂层制备成本大大降低。2) The amount of precious metals in the coating is significantly reduced, and at the same time, the preparation method of the non-noble metal coating is simple, so the coating preparation cost is greatly reduced.
3)本发明对提高燃料电池金属双极板性能、推进燃料电池产业化进程具有重要意义。3) The invention is of great significance for improving the performance of fuel cell metal bipolar plates and advancing the industrialization process of fuel cells.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1、2制备得到的涂层的整体结构示意图；1 is a schematic diagram of the overall structure of the coating prepared in Examples 1 and 2;
图2为实施例3制备得到的涂层的整体结构示意图；2 is a schematic diagram of the overall structure of the coating prepared in Example 3;
图3为实施例5制备得到的涂层的整体结构示意图；3 is a schematic diagram of the overall structure of the coating prepared in Example 5;
图4为实施例1-5及纯金薄膜制备得到的涂层接触电阻测量结果图；FIG. 4 is a graph of measurement results of contact resistance of the coatings prepared in Examples 1-5 and a pure gold thin film; FIG.
图5为实施例1-5制备得到的涂层及纯金薄膜在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。 FIG. 5 is a current density of 1.60 V (vs SHE) potentiostatic polarization for 1 h in the coating and the pure gold thin film prepared in Examples 1-5 in a H 2 SO 4 (containing 0.1 ppm HF) solution at pH = 3 and 80 ° C. curve.
图中标记说明：Description of the marks in the figure:
1—金属双极板、2—耐蚀非贵金属层、3—贵金属层、4—非贵金属填充物、5—气体扩散层。1—metal bipolar plate, 2—corrosion-resistant non-precious metal layer, 3—precious metal layer, 4—non-precious metal filler, 5—gas diffusion layer.
具体实施方式detailed description
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施，给出了详细的实施方法和具体的操作过程，但本发明的保护范围不限于下属的实施例。The present invention is described in detail below with reference to the drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the subordinate embodiments.
实施例1Example 1
采用低成本掺杂方法制备用于燃料电池金属双极板导电耐蚀涂层的方法包括以下步骤：A method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1放入单腔体磁控溅射镀膜机炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除金属双极板1表面金属氧化成，提高表面清洁度，进而提高膜基结合力；1) Use a cleaning agent to clean the surface of the metal bipolar plate 1 for oil and impurities, and place the cleaned metal bipolar plate 1 into the furnace cavity of a single-chamber magnetron sputtering coating machine, and then control the vacuum degree of the furnace cavity. After reaching the set value, the ion source is turned on to generate plasma to bombard the surface of the metal bipolar plate 1 to remove the oxidation of the metal on the surface of the metal bipolar plate 1 to improve the surface cleanliness and thus the adhesion of the film base;
2)在第一步处理后的金属双极板1表面预先沉积100nm的耐蚀金属Ti打底层2，提高涂层耐腐蚀性并提高膜基结合力；2) 100 nm of anti-corrosive metal Ti base layer 2 is deposited on the surface of the metal bipolar plate 1 after the first treatment to improve the corrosion resistance of the coating and improve the adhesion of the film base;
3)在第二步沉积的耐蚀金属打底层2表面通过磁控溅射的方法共同溅射Au靶材及Ti靶材，并通过工艺参数的控制调控涂层中贵金属3与非贵金属4成分的比例，控制工艺时间保证沉积涂层厚度为50nm；3) The second layer of the anti-corrosive metal deposited in the second step was sputtered together with the Au target and the Ti target by magnetron sputtering, and the precious metal 3 and non-noble metal 4 components in the coating were adjusted by controlling the process parameters. Control the process time to ensure that the thickness of the deposited coating is 50nm;
4)图1所示为该涂层结构，如图5所示为该涂层在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。图4为所得涂层接触电阻测量结果图。 4) Figure 1 shows the coating structure, and Figure 5 shows the coating at 1.60 V (vs SHE) potentiostatic electrode in a H 2 SO 4 (containing 0.1 ppm HF) solution at pH = 3 and 80 ° C. 1h current density curve. FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
可以看出，相较于纯金薄膜，该实施例中制备得到的涂层初始接触电阻为1.52mΩ·cm 2，导电性能基本不变，pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h腐蚀电流密度稳定在6.6E-7A/cm 2，耐腐蚀性提升。因此，通过该掺杂方案可在保证涂层性能的前提下降低贵金属用量，从而降低涂层制备成本。 It can be seen that compared with the pure gold thin film, the initial contact resistance of the coating prepared in this example is 1.52 mΩ · cm 2 , and the conductivity is basically unchanged. PH = 3 , 80 ° C H 2 SO 4 (containing 0.1 (ppm HF) solution 1.60V (vs SHE) constant potential polarization 1h corrosion current density is stable at 6.6E-7A / cm 2 , corrosion resistance is improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
实施例2Example 2
采用低成本掺杂方法制备用于燃料电池金属双极板导电耐蚀涂层的方法包括以下步骤：A method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1放入单腔体磁控溅射镀膜机炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除金属双极板1表面金属氧化成，提高表面清洁度，进而提高膜基结合力；1) Use a cleaning agent to clean the surface of the metal bipolar plate 1 for oil and impurities, and place the cleaned metal bipolar plate 1 into the furnace cavity of a single-chamber magnetron sputtering coating machine, and then control the vacuum degree of the furnace cavity. After reaching the set value, the ion source is turned on to generate plasma to bombard the surface of the metal bipolar plate 1 to remove the oxidation of the metal on the surface of the metal bipolar plate 1 to improve the surface cleanliness and thus the adhesion of the film base;
2)在第一步处理后的金属双极板1表面预先沉积100nm的耐蚀金属Ti打 底层2，提高涂层耐腐蚀性并提高膜基结合力；2) 100 nm of anti-corrosive metal Ti base layer 2 is deposited on the surface of the metal bipolar plate 1 after the first treatment to improve the corrosion resistance of the coating and improve the adhesion of the film base;
3)在第二步沉积的耐蚀金属打底层2表面通过磁控溅射的方法溅射Au靶材，同时通过反应溅射的方法沉积TiC，并通过工艺参数的控制调控涂层中贵金属3与非贵金属4成分的比例，控制工艺时间保证沉积涂层厚度为100nm；3) The second layer of the anti-corrosive metal deposited in the second step was sputtered on the Au target by magnetron sputtering, while TiC was deposited by reactive sputtering, and the precious metals in the coating were controlled by the control of process parameters. Proportion to 4 components of non-precious metal, control the process time to ensure the thickness of the deposited coating is 100nm;
4)图1所示为该涂层结构，如图5所示为该涂层在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。图4为所得涂层接触电阻测量结果图。 4) Figure 1 shows the coating structure, and Figure 5 shows the coating at 1.60 V (vs SHE) potentiostatic electrode in a H 2 SO 4 (containing 0.1 ppm HF) solution at pH = 3 and 80 ° C. 1h current density curve. FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
可以看出，相较于纯金薄膜，该实施例中制备得到的涂层初始接触电阻为1.64mΩ·cm 2，导电性能基本不变，pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h腐蚀电流密度稳定在8.5E-7A/cm 2，耐腐蚀性提升。因此，通过该掺杂方案可在保证涂层性能的前提下降低贵金属用量，从而降低涂层制备成本。 It can be seen that the initial contact resistance of the coating prepared in this example is 1.64 mΩ · cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged. H 2 SO 4 (containing 0.1 at pH = 3 and 80 ° C) (ppm HF) solution 1.60V (vs SHE) constant potential polarization 1h corrosion current density is stable at 8.5E-7A / cm 2 , corrosion resistance is improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
实施例3Example 3
采用低成本掺杂方法制备用于燃料电池金属双极板导电耐蚀涂层的方法包括以下步骤：A method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1放入连续式磁控溅射镀膜机炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除金属双极板1表面金属氧化成，提高表面清洁度，进而提高膜基结合力；1) Use a cleaning agent to clean the surface of the metal bipolar plate 1 for oil and impurities, and place the cleaned metal bipolar plate 1 into the furnace chamber of a continuous magnetron sputtering coating machine, and then control the vacuum degree of the furnace chamber until the vacuum degree reaches After setting the value, the ion source is turned on to generate plasma to bombard the surface of the metal bipolar plate 1 to remove the oxidation of the metal on the surface of the metal bipolar plate 1 to improve the surface cleanliness and thus the adhesion of the film base;
2)在第一步处理后的金属双极板表面1预先沉积20nm的耐蚀金属Cr打底层2，提高涂层耐蚀性并提高膜基结合力；2) On the surface of the metal bipolar plate 1 after the first treatment, a 20 nm corrosion-resistant metal Cr is deposited on the base layer 2 in advance to improve the corrosion resistance of the coating and improve the adhesion of the film base;
3)在第二步沉积的耐蚀金属打底层2表面沉积贵金属Au涂层10nm；3) deposit a precious metal Au coating layer 10nm on the surface of the corrosion-resistant metal substrate 2 deposited in the second step;
4)在第三步沉积涂层的表面重复步骤2；4) Repeat step 2 on the surface where the coating is deposited in the third step;
5)在第四步沉积涂层的表面重复步骤3；5) Repeat step 3 on the surface where the coating is deposited in the fourth step;
6)图2所示为该涂层结构，如图5所示为该涂层在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。图4为所得涂层接触电阻测量结果图。 6) Figure 2 shows the coating structure, and Figure 5 shows the coating at 1.60V (vs SHE) potentiostatic electrode in a H 2 SO 4 (containing 0.1 ppm HF) solution at pH = 3 and 80 ° C. 1h current density curve. FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
可以看出，相较于纯金薄膜，该实施例中制备得到的涂层初始接触电阻为 1.66mΩ·cm 2，导电性能基本不变，pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h腐蚀电流密度稳定在1.3E-7A/cm 2，耐腐蚀性明显提升。因此，通过该掺杂方案可在保证涂层性能的前提下降低贵金属用量，从而降低涂层制备成本。 It can be seen that the initial contact resistance of the coating prepared in this example is 1.66 mΩ · cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged. The pH is 3 at 80 ° C and H 2 SO 4 (containing 0.1 The corrosion current density in the 1.60V (vs SHE) constant potential polarization for 1h in the solution of ppm (HF) was stable at 1.3E-7A / cm 2 , and the corrosion resistance was significantly improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
实施例4Example 4
采用低成本掺杂方法制备用于燃料电池金属双极板导电耐蚀涂层的方法包括以下步骤：A method for preparing a conductive corrosion-resistant coating for a fuel cell metal bipolar plate by a low-cost doping method includes the following steps:
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1放入连续式磁控溅射镀膜机炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除金属双极板1表面金属氧化成，提高表面清洁度，进而提高膜基结合力；1) Use a cleaning agent to clean the surface of the metal bipolar plate 1 for oil and impurities, and place the cleaned metal bipolar plate 1 into the furnace chamber of a continuous magnetron sputtering coating machine, and then control the vacuum degree of the furnace chamber until the vacuum degree reaches After setting the value, the ion source is turned on to generate plasma to bombard the surface of the metal bipolar plate 1 to remove the oxidation of the metal on the surface of the metal bipolar plate 1 to improve the surface cleanliness and thus the adhesion of the film base;
2)在第一步处理后的金属双极板表面1预先沉积20nm的耐蚀金属Cr打底层2，提高涂层耐蚀性并提高膜基结合力；2) On the surface of the metal bipolar plate 1 after the first treatment, a 20 nm corrosion-resistant metal Cr is deposited on the base layer 2 in advance to improve the corrosion resistance of the coating and improve the adhesion of the film base;
3)在第二步沉积的耐蚀金属打底层2表面沉积非晶碳涂层30nm；3) deposit an amorphous carbon coating 30 nm on the surface of the corrosion-resistant metal substrate 2 deposited in the second step;
4)在第三步沉积涂层的表面沉积Ag涂层10nm；4) depositing a 10 nm Ag coating on the surface of the third step deposition coating;
5)在第四步沉积涂层的表面重复步骤3；5) Repeat step 3 on the surface where the coating is deposited in the fourth step;
6)在第四步沉积涂层的表面重复步骤4；6) Repeat step 4 on the surface where the coating is deposited in the fourth step;
7)在第四步沉积涂层的表面重复步骤3；7) Repeat step 3 on the surface where the coating is deposited in the fourth step;
8)在第四步沉积涂层的表面重复步骤4；8) Repeat step 4 on the surface where the coating is deposited in the fourth step;
9)如图5所示为该涂层在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。图4为所得涂层接触电阻测量结果图。 9) As shown in FIG. 5, the current density curve of the coating at 1.60 V (vs SHE) constant potential polarization for 1 h in H 2 SO 4 (containing 0.1 ppm HF) solution at pH = 3 and 80 ° C. is shown. FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
可以看出，相较于纯金薄膜，该实施例中制备得到的涂层初始接触电阻为1.86mΩ·cm 2，导电性能基本不变，pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h腐蚀电流密度稳定在5.8E-7A/cm 2，耐腐蚀性略有提升。因此，通过该掺杂方案可在保证涂层性能的前提下降低贵金属用量，从而降低涂层制备成本。 It can be seen that the initial contact resistance of the coating prepared in this example is 1.86 mΩ · cm 2 compared to a pure gold thin film, and the conductivity is basically unchanged. H 2 SO 4 (containing 0.1 at pH = 3 and 80 ° C) The corrosion current density is stable at 5.8E-7A / cm 2 at 1.60V (vs SHE) constant potential polarization for 1h in the solution of ppm HF), and the corrosion resistance is slightly improved. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
实施例5Example 5
用于燃料电池金属双极板的低成本、高导电、耐腐蚀贵金属涂层的制备方法包括以下步骤：A method for preparing a low-cost, highly conductive, and corrosion-resistant precious metal coating for a fuel cell metal bipolar plate includes the following steps:
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1放入连续式磁控溅射镀膜机炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除金属双极板1表面金属氧化成，提高表面清洁度，进而提高膜基结合力；1) Use a cleaning agent to clean the surface of the metal bipolar plate 1 for oil and impurities, and place the cleaned metal bipolar plate 1 into the furnace chamber of a continuous magnetron sputtering coating machine, and then control the vacuum degree of the furnace chamber until the vacuum degree reaches After setting the value, the ion source is turned on to generate plasma to bombard the surface of the metal bipolar plate 1 to remove the oxidation of the metal on the surface of the metal bipolar plate 1 to improve the surface cleanliness and thus the adhesion of the film base;
2)在第一步处理后的金属双极板1所有表面预先沉积30nm的耐蚀金属Ti层，提高涂层耐蚀性；2) A 30 nm layer of corrosion-resistant metal Ti is deposited on all surfaces of the metal bipolar plate 1 after the first treatment to improve the corrosion resistance of the coating;
3)在贵金属Au溅射沉积的腔体中，通过掩膜遮挡金属双极板槽所在位置，而后在第二步沉积的耐蚀金属层2表面通过磁控溅射的方法溅射Au靶材，只在金属双极板与气体扩散层接触的位置镀覆Au涂层30nm，待掩膜表面积累较多贵金属时，将其取下以回收利用为镀覆在极板表面的贵金属，从而降低涂层成本；3) In the cavity deposited by precious metal Au sputtering, the position of the metal bipolar plate slot is shielded by a mask, and then the target of the corrosion-resistant metal layer 2 deposited in the second step is sputtered by a magnetron sputtering method. The Au coating is plated only at the position where the metal bipolar plate is in contact with the gas diffusion layer. When more precious metal accumulates on the surface of the mask, it is removed for recycling as a precious metal plated on the surface of the electrode, thereby reducing Coating cost
4)图2所示为该涂层结构，如图5所示为该涂层在pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h电流密度曲线。图4为所得涂层接触电阻测量结果图。 4) Figure 2 shows the coating structure, and Figure 5 shows the coating at 1.60V (vs SHE) potentiostatic electrode in H 2 SO 4 (containing 0.1ppm HF) solution at pH = 3 and 80 ° C. 1h current density curve. FIG. 4 is a graph showing the measurement results of the contact resistance of the obtained coating.
可以看出，相较于纯金薄膜，该实施例中制备得到的涂层初始接触电阻为1.98mΩ·cm 2，导电性能略有下降，pH＝3、80℃的H 2SO 4(含0.1ppm HF)溶液中1.60V(vs SHE)恒电位极化1h腐蚀电流密度稳定在1.5E-6A/cm 2，耐腐蚀性略有下降，但该涂层依旧具有较优性能。因此，通过该掺杂方案可在保证涂层性能的前提下降低贵金属用量，从而降低涂层制备成本。 It can be seen that the initial contact resistance of the coating prepared in this example is 1.98 mΩ · cm 2 compared to a pure gold thin film, and the conductivity is slightly reduced. The pH is 3 at 80 ° C for H 2 SO 4 (containing 0.1 The corrosion current density is stable at 1.5E-6A / cm 2 at 1.60V (vs SHE) constant potential polarization in a solution of 1.60V (vs SHE) in a ppm HF) solution, but the corrosion resistance slightly decreases, but the coating still has superior performance. Therefore, this doping scheme can reduce the amount of precious metals while ensuring the performance of the coating, thereby reducing the cost of coating preparation.
上述的对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is to facilitate understanding and use of the invention by those skilled in the art. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments and the general principles described herein can be applied to other embodiments without creative effort. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art based on the disclosure of the present invention, and improvements and modifications made without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (10)

  1. 一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，该涂层由贵金属部分及导电耐蚀的非贵金属部分组成，其中贵金属在涂层中所占比例为10-90wt％。A conductive corrosion-resistant coating for a fuel cell metal bipolar plate is characterized in that the coating is composed of a precious metal part and a conductive and corrosion-resistant non-precious metal part, wherein the proportion of the precious metal in the coating is 10-90 wt%.
  2. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的非贵金属部分作为填充物随机嵌入贵金属部分形成涂层。The conductive corrosion-resistant coating for a metal bipolar plate of a fuel cell according to claim 1, wherein the non-noble metal portion is randomly embedded in the noble metal portion as a filler to form a coating.
  3. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的非贵金属部分与贵金属部分交替布置在双极板表面形成多层涂层结构。The conductive corrosion-resistant coating for a fuel cell metal bipolar plate according to claim 1, wherein the non-noble metal portion and the noble metal portion are alternately arranged on the surface of the bipolar plate to form a multilayer coating structure.
  4. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的涂层由在带有流道的金属双极板与气体扩散层接触部位镀覆贵金属涂层，在非接触部位镀覆非贵金属涂层构成。The conductive and corrosion-resistant coating for a metal bipolar plate of a fuel cell according to claim 1, wherein the coating is plated on a contact portion between the metal bipolar plate with a flow channel and a gas diffusion layer. Precious metal coating consists of non-precious metal coating on non-contact parts.
  5. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的贵金属部分包括Au、Ag、Ru、Rh、Pd、Os、Ir或Pt。The conductive corrosion-resistant coating for a metal bipolar plate of a fuel cell according to claim 1, wherein the precious metal portion comprises Au, Ag, Ru, Rh, Pd, Os, Ir or Pt.
  6. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的非贵金属部分包括金属单质或非金属单质，或金属化合物。The conductive corrosion-resistant coating for a metal bipolar plate of a fuel cell according to claim 1, wherein the non-noble metal portion comprises a metal element or a non-metal element or a metal compound.
  7. 根据权利要求6所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的金属单质包括Ti、Cr、W、Zr、Nb、Ta或Mo，所述的非金属单质包括C、N、H或O，所述的金属化合物为前述金属单质和非金属单质组成的金属化合物。The conductive and anticorrosive coating for a metal bipolar plate of a fuel cell according to claim 6, characterized in that said single element of metal comprises Ti, Cr, W, Zr, Nb, Ta or Mo, and said non- The metal element includes C, N, H or O, and the metal compound is a metal compound composed of the foregoing metal element and non-metal element.
  8. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的非贵金属部分在涂层中所占的比例为10-90wt％。The conductive corrosion-resistant coating for a fuel cell metal bipolar plate according to claim 1, wherein the proportion of the non-noble metal portion in the coating is 10-90 wt%.
  9. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的导电耐蚀涂层通过单腔体磁控溅射镀膜设备制备，或通过连续式磁控溅射镀膜设备制备。The conductive anticorrosive coating for a metal bipolar plate of a fuel cell according to claim 1, wherein the conductive anticorrosive coating is prepared by a single-chamber magnetron sputtering coating device, or by a continuous type Preparation of magnetron sputtering coating equipment.
  10. 根据权利要求1所述的一种燃料电池金属双极板用导电耐蚀涂层，其特征在于，所述的导电耐蚀涂层的厚度为10-200nm。The conductive corrosion-resistant coating for a fuel cell metal bipolar plate according to claim 1, wherein the thickness of the conductive corrosion-resistant coating is 10-200 nm.
PCT/CN2019/072824 2018-08-31 2019-01-23 Conductive corrosion-resistant coating for metal bipolar plate of fuel cell WO2020042535A1 (en)

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