WO2024066057A1 - 一种表面改性的燃料电池双极板、制备方法及燃料电池 - Google Patents

一种表面改性的燃料电池双极板、制备方法及燃料电池 Download PDF

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WO2024066057A1
WO2024066057A1 PCT/CN2022/138193 CN2022138193W WO2024066057A1 WO 2024066057 A1 WO2024066057 A1 WO 2024066057A1 CN 2022138193 W CN2022138193 W CN 2022138193W WO 2024066057 A1 WO2024066057 A1 WO 2024066057A1
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Prior art keywords
bipolar plate
fuel cell
target
target material
modified fuel
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PCT/CN2022/138193
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English (en)
French (fr)
Inventor
李松
李伟民
王赛强
唐玮
苑欣业
俞深
赵晨晨
祁同庆
马明
宁德
杨春雷
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深圳先进技术研究院
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Publication of WO2024066057A1 publication Critical patent/WO2024066057A1/zh

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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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 present application relates to the field of fuel cell technology, and in particular to a surface-modified fuel cell bipolar plate, a preparation method and a fuel cell.
  • metal bipolar plates have good mechanical properties, mechanical processing properties and dimensional stability, and can be prepared into metal sheets by rolling, thereby significantly reducing the mass and volume of the battery.
  • metal materials have mature processing technology, and precision processing technology can be used to process the required flow channels for cooling and drainage. Because of this, metal bipolar plates are considered to be ideal bipolar plate electrode materials.
  • Stainless steel materials are highly competitive among metal bipolar plate materials due to their high corrosion resistance, high thermal conductivity, good processing performance, and low price.
  • studies have found that untreated stainless steel bipolar plates are prone to produce oxide passivation films on their surfaces in the PEMFC environment.
  • the poor conductivity of the oxide passivation film will significantly increase the contact resistance.
  • the electrolyte will also be contaminated by metal ions such as nickel, chromium, and iron precipitated from the bipolar plates.
  • the ohmic impedance and charge transfer impedance of the battery will increase significantly, directly affecting the service life of the fuel cell and failing to meet the high performance requirements of the fuel cell.
  • the stainless steel bipolar plates modified by coating can improve the corrosion resistance of the bipolar plates while ensuring good conductivity, thereby ensuring the overall battery performance and life.
  • the performance of stainless steel bipolar plates after different surface coating modifications varies.
  • researchers at home and abroad have conducted a large number of studies on stainless steel surface modification.
  • it can be divided into two types of materials: metal-based coatings and carbon-based coatings.
  • the corrosion resistance of the stainless steel bipolar plate can be significantly improved while retaining its high conductivity, mechanical properties and low permeability.
  • the preparation is simple and the cost is low.
  • the carbon-based coating exhibits good hydrophobic properties, which is conducive to the timely discharge of liquid water inside the fuel cell.
  • improving density and reducing internal pressure stress have not been achieved at the same time.
  • the production of defect-free, low internal stress and stable performance carbon-based coatings has become a technical challenge.
  • One of the purposes of the present application is to provide a surface-modified fuel cell bipolar plate, comprising a bipolar plate and a C—Cr coating formed on the surface of the bipolar plate.
  • the bipolar plate is 316 stainless steel foil.
  • the C—Cr coating has a thickness of 800-1000 nm.
  • the second object of the present application is to provide a method for preparing the surface-modified fuel cell bipolar plate, comprising the following steps:
  • the bipolar plate is placed on an anode frame, and a cathode frame is arranged in a parallel direction to the anode frame, a target is arranged on the cathode frame, the target and the bipolar plate are arranged opposite to each other, and the target is a solid C-Cr twin target;
  • the cathode frame is connected to a high-voltage power supply, and the high-voltage power supply excites the target atoms in the target material into a particle state.
  • the excited particles move along the direction of the bipolar plate and are deposited on the bipolar plate.
  • the working gas in the step of introducing a working gas into a vacuum environment, is argon or a mixture of hydrogen and argon.
  • the step of introducing the working gas in the vacuum environment specifically includes: evacuating the coating chamber and introducing the working gas, wherein the evacuation is performed so that the body pressure is maintained below 1*10 ⁇ 3 Pa to ensure the quality of the workpiece, and the working pressure range is 0.3-0.8Pa after the working gas is introduced, and different effects of the workpiece are achieved by adjusting different pressures.
  • the bipolar plate in the environment of the above-mentioned working gas, is placed on an anode frame, and a cathode frame is arranged in a parallel direction to the anode frame, a target material is arranged on the cathode frame, and the target material and the bipolar plate are arranged opposite to each other.
  • the distance between the target material and the bipolar plate is 100 to 150 mm, ensuring that the coating grows within the range of glow discharge and the coating grows uniformly.
  • the bipolar plate in the working gas environment, is placed on an anode rack, a cathode rack is arranged in a parallel direction to the anode rack, a target is arranged on the cathode rack, the target and the bipolar plate are arranged oppositely, and in the step where the target is a solid C:Cr twin target, the target specification is 600mm*100mm*5mm, and the surface area of the twin target is 1200cm2 .
  • the high voltage power supply excites the target atoms in the target material into a particle state, and the excited particles move along the bipolar plate and deposit on the bipolar plate, the power range of the high voltage power supply is 5-9kW, and the power density range is 4.17-7.5W/ cm2 .
  • the high-voltage power supply excites the target atoms in the target material into a particle state, and the excited particles move along the direction of the bipolar plate and are deposited on the bipolar plate, the deposition temperature range is 20-300°C, and the coating adhesion can be changed by adjusting the temperature.
  • the high-voltage power supply excites the target atoms in the target material into a particle state, and the excited particles move along the direction of the bipolar plate and are deposited on the bipolar plate.
  • the deposition time is 30-40 minutes, and the deposition time corresponds to the film thickness, and coatings of different thicknesses can be obtained.
  • the third object of the present application is to provide a fuel cell, comprising the surface-modified fuel cell bipolar plate.
  • the surface-modified fuel cell bipolar plate and preparation method provided in the present application use the bipolar plate of the fuel cell as the substrate, and utilize vacuum sputtering coating technology to form a uniform C-Cr coating on the surface of the substrate.
  • Cr-doped C the defects of poor adhesion between stainless steel and C film and some difficulties in carbon deposition are overcome.
  • C-Cr film can improve the interface conductivity and corrosion resistance of the coating, while enabling the film to obtain low residual stress and good stability, and reduce the risk of local corrosion from coating defects.
  • FIG1 is a schematic diagram of the structure of a surface-modified fuel cell bipolar plate provided in an embodiment of the present application.
  • FIG. 2 is a flow chart showing the steps of the method for preparing the surface-modified fuel cell bipolar plate provided in an embodiment of the present application.
  • first and second are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, a feature defined as “first” or “second” may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of “plurality” is two or more, unless otherwise clearly and specifically defined.
  • FIG. 1 is a schematic structural diagram of a surface-modified fuel cell bipolar plate provided in one embodiment of the present application, including: a bipolar plate 110 and a C—Cr coating 120 formed on the surface of the bipolar plate 110 .
  • the bipolar plate 110 is 316 stainless steel foil.
  • the thickness of the C—Cr coating 120 is 800-1000 nm, so as to obtain the required contact resistance and corrosion current.
  • the surface-modified fuel cell bipolar plate provided in the above-mentioned embodiments of the present application overcomes the defects of poor adhesion between stainless steel and C film and some difficulties in carbon deposition by using Cr-doped C.
  • C-Cr film can improve the interfacial conductivity and corrosion resistance of the coating, while enabling the film to obtain low residual stress and good stability, and reduce the risk of local corrosion originating from coating defects.
  • the surface-modified fuel cell bipolar plate taken the bipolar plate of the fuel cell as the substrate, and forms a uniform C-Cr coating on the surface of the substrate by using vacuum sputtering coating technology.
  • C doped with Cr element the defects of poor adhesion between stainless steel and C film and some difficulties in carbon deposition are overcome.
  • C-Cr film can improve the interface conductivity and corrosion resistance of the coating, while enabling the film to obtain low residual stress and good stability, and reduce the risk of local corrosion caused by coating defects.
  • FIG. 2 is a flow chart of the steps of the method for preparing the surface-modified fuel cell bipolar plate provided in an embodiment of the present application, including the following steps S110 to S130 , and the implementation method of each step is described in detail below.
  • Step S110 introducing working gas into the vacuum environment.
  • the working gas is argon or a mixture of hydrogen and argon.
  • the step of introducing the working gas in the vacuum environment specifically includes: evacuating the coating chamber and introducing the working gas, the pressure is maintained below 1*10 ⁇ 3 Pa during evacuation, and the pressure is maintained at 0.3-0.8Pa after the working gas is introduced, and different effects of the workpiece are achieved by adjusting different pressures.
  • Step S120 In the working gas environment, the bipolar plate is placed on an anode rack, and a cathode rack is arranged in a parallel direction to the anode rack. A target is arranged on the cathode rack. The target and the bipolar plate are arranged opposite to each other, and the target is a solid C:Cr twin target.
  • the distance between the target and the bipolar plate is 100-150 mm, ensuring that the coating grows within the range of glow discharge and the coating grows uniformly.
  • the target material has a size of 600 mm*100 mm*5 mm, and the surface area of the twin target material is 1200 cm 2 .
  • the equipment used is a medium frequency magnetron sputtering equipment
  • the target material used for sputtering is a C-Cr (20-80% at.) twin target.
  • the target material utilization rate can be as high as more than 70%, and the target material has a longer service life and a faster sputtering rate.
  • Step S130 connecting the cathode frame to a high-voltage power supply, which excites the target atoms in the target material into a particle state, and the excited particles move along the direction of the bipolar plate and are deposited on the bipolar plate.
  • the power of the high voltage power source is in the range of 5-9 kW, and the power density is in the range of 4.17-7.5 w/cm 2 .
  • the deposition temperature is 20-300° C., and the coating adhesion can be changed by adjusting the temperature.
  • the deposition time is 30-40 minutes.
  • the deposition time corresponds to the film thickness, and coatings of different thicknesses can be obtained.
  • the above embodiment of the present application adopts the principle of medium frequency sputtering to form a C-Cr coating on the surface of the bipolar plate. Due to the use of a twin target sputtering system, the target material utilization rate is high, the service life is longer, the sputtering rate is faster, and the target material poisoning phenomenon can be eliminated.
  • the medium frequency magnetron sputtering can obtain a smooth and dense film with high hardness and linear film thickness growth.
  • Multi-arc sputtering applies a small voltage and a large current to the target material to ionize the material (positively charged particles), thereby striking the substrate (negatively charged) at high speed and depositing.
  • the target material in a particle state reacts chemically with the working gas, and the grains nucleate and grow to form a dense C:Cr film.
  • the surface-modified fuel cell bipolar plate taken the bipolar plate of the fuel cell as the substrate, and forms a uniform C-Cr coating on the surface of the substrate by using vacuum sputtering coating technology.
  • C doped with Cr element the defects of poor adhesion between stainless steel and C film and some difficulties in carbon deposition are overcome.
  • C-Cr film can improve the interface conductivity and corrosion resistance of the coating, while enabling the film to obtain low residual stress and good stability, and reduce the risk of local corrosion caused by coating defects.
  • the surface resistance can be adjusted by introducing different flow rates of H 2 to obtain a coating with desired conductive properties.
  • the surface-modified fuel cell bipolar plate and preparation method thereof provided in the above-mentioned embodiments of the present application take the bipolar plate of the fuel cell as the substrate, and utilize vacuum sputtering coating technology to form a uniform C-Cr coating on the surface of the substrate.
  • C doped with Cr element the defects of poor adhesion between stainless steel and C film and some difficulties in carbon deposition are overcome.
  • C-Cr film can improve the interface conductivity and corrosion resistance of the coating, while enabling the film to obtain low residual stress and good stability, and reduce the risk of local corrosion originating from coating defects.

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Abstract

本申请提供的表面改性的燃料电池双极板及其制备方法，以燃料电池的双极板为基材，利用真空溅射镀层技术在所述基材的表面形成均匀的C-Cr涂层，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。另外，本申请还提供了一种燃料电池。

Description

一种表面改性的燃料电池双极板、制备方法及燃料电池 技术领域
本申请涉及燃料电池技术领域，特别涉及一种表面改性的燃料电池双极板、制备方法及燃料电池。
 背景技术
目前国内外制备质子交换膜燃料电池（PEMFC）双极板多采用碳基材料，尽管碳基材料的成本不高，但是由于双极板表面复杂气体流道的要求，制备碳基双极板所需的机械加工费用较高。同时，碳基材料的抗弯能力较差、质脆，该类双极板的厚度较大。因此，碳基双极板的体积、质量和成本占了整个电池堆的绝大部分。较碳基双极板而言，金属材料双极板具有良好的力学性能、机械加工性能和尺寸稳定性，可通过轧制，制备成金属薄片，从而显著降低电池质量和体积。与此同时，金属材料具备成熟的加工工艺，可利用精密加工技术，加工出所需的流道，便于冷却、排水。正因为如此，金属材料双极板被认为是理想的双极板电极材料。
不锈钢材料具有的高耐蚀性、高导热性、良好的加工性能、价格低等特点，在金属双极板材料中极具竞争力。然而，经研究发现，未经处理的不锈钢双极板在PEMFC的环境中容易在其表面产生氧化物钝化膜，氧化物钝化膜的导电性较差会明显增大接触电阻，此外电解液也会因双极板析出的镍、铬、铁等金属离子受到污染，电池的欧姆阻抗和电荷转移阻抗会明显增大，直接影响到燃料电池的使用寿命，无法满足燃料电池的高性能需求。未经表面处理的不锈钢双极板，虽具有生产快、加工成本低的优势，但不锈钢材料在电池环境中出现的耐蚀性较差、易产生钝化膜等问题直接影响到了燃料电池的使用性能。为此，通过表面改性处理提高不锈钢双极板的耐蚀性是解决其商业化应用的重要途径。
目前，能同时解决不锈钢双极板的导电性与耐蚀性问题的最有效方法是表面进行涂层改性，经过涂层改性后的不锈钢双极板能在保证良好导电性的同时提高双极板的耐蚀性，保障整体电池的使用性能和寿命。不锈钢双极板不同的表面涂层改性后表现出的性能各有差异。针对不锈钢双极板涂层性能需求，国内外研究人员进行了大量的不锈钢表面改性研究。依据涂层的材料不同，可分为金属基涂层和碳基涂层这两类材料。
将碳基和金属的优点相结合，通过在不锈钢双极板表面沉积制备碳基镀层，可在保留不锈钢双极板较高导电性、力学性能和低渗透性的基础上，显著提升其耐蚀性，且制备简单，成本较低。同时碳基涂层表现出良好的疏水性能，有利于及时排出燃料电池内部的液态水。然而，对于碳基薄膜来说，提高致密性和降低内压应力一直无法同时实现，生产无缺陷、低内应力和性能稳定的碳基涂层成为了一项技术难题。
 技术问题
鉴于此，有必要针对现有技术中存在的缺陷提供一种可以提高致密性和降低内压应力的表面改性的燃料电池双极板、制备方法及燃料电池。
 技术解决方案
为解决上述问题，本申请采用下述技术方案：
本申请目的之一，提供了一种表面改性的燃料电池双极板，包括双极板及形成于所述双极板表面的C-Cr涂层。
在其中一些实施例中，所述双极板为316不锈钢箔。
在其中一些实施例中，所述C-Cr涂层的厚度为800-1000nm。
本申请目的之二，提供了一种所述的表面改性的燃料电池双极板的制备方法，包括下述步骤：
在真空环境中通入工作气体；
于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C-Cr孪生靶；
将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上。
在其中一些实施例中，在真空环境中通入工作气体的步骤中，所述工作气体为氩气或氢气与氩气的混合气体。
在其中一些实施例中，在真空环境中通入工作气体的步骤中，具体包括：在镀膜室内抽真空，并通入工作气体，抽真空使得本体压强保持在1*10 ‑ 3Pa以下，保证制件质量，通入工作气体后工作压强范围在0.3-0.8Pa，通过调节不同压强以达到制件的不同效果。
在其中一些实施例中，在于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶的步骤中，所述靶材和所述双极板的距离在100～150mm，保证涂层生长在辉光放电的范围内，涂层生长均匀。
在其中一些实施例中，在于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶的步骤中，靶材规格为600mm*100mm*5mm，孪生靶材表面积为1200cm 2。
在其中一些实施例中，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述高压电源的功率范围在5-9kW，功率密度范围在4.17-7.5W/cm 2。
在其中一些实施例中，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述沉积的温度范围为20-300℃，通过调节温度可实现涂层附着力的变化。
在其中一些实施例中，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述沉积的时间为30-40min，沉积时间对应薄膜厚度，可获得不同厚度的涂层。
本申请目的之三，提供了一种燃料电池，包括所述表面改性的燃料电池双极板。
 有益效果
本申请采用上述技术方案，其有益效果如下：
本申请提供的表面改性的燃料电池双极板及其制备方法，以燃料电池的双极板为基材，利用真空溅射镀层技术在所述基材的表面形成均匀的C-Cr涂层，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。
 附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的表面改性的燃料电池双极板的结构示意图。
图2为本申请实施例提供的所述的表面改性的燃料电池双极板的制备方法的步骤流程图。
 本发明的实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。
在本申请的描述中，需要理解的是，术语“上”、“下”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。
请参阅图1，为本申请一实施例提供的一种表面改性的燃料电池双极板的结构示意图，包括：双极板110及形成于所述双极板110表面的C-Cr涂层120。
在其中一些实施例中，所述双极板110为316不锈钢箔。
在其中一些实施例中，所述C-Cr涂层120的厚度为800-1000nm，从而可以获得达到要求的接触电阻和腐蚀电流。
本申请上述实施例提供的表面改性的燃料电池双极板，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。
本申请上述实施例提供的表面改性的燃料电池双极板，以燃料电池的双极板为基材，利用真空溅射镀层技术在所述基材的表面形成均匀的C-Cr涂层，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。
请参阅图2，为本申请实施例提供的所述的表面改性的燃料电池双极板的制备方法的步骤流程图，包括下述步骤S110至步骤S130，以下详细说明各个步骤的实现方式。
步骤S110：在真空环境中通入工作气体。
在其中一些实施例中，所述工作气体为氩气或氢气与氩气的混合气体。
具体地，在真空环境中通入工作气体的步骤中，具体包括：在镀膜室内抽真空，并通入工作气体，抽真空时压力保持在1*10 ‑ 3Pa以下，通入工作气体后压力保持在0.3-0.8Pa，通过调节不同压强以达到制件的不同效果。
步骤S120：于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶。
在其中一些实施例中，所述靶材和所述双极板的距离在100～150mm，保证涂层生长在辉光放电的范围内，涂层生长均匀。
在其中一些实施例中，所述靶材的规格为600mm*100mm*5mm，孪生靶材表面积为1200cm 2。
在其中一些实施例中，使用设备为中频磁控溅射设备，溅射所用靶材为C-Cr (20-80 % at.)孪生靶，靶材利用率最高可达70%以上，靶材有更长的使用寿命，更快的溅射速率。
步骤S130：将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上。
在其中一些实施例中，所述高压电源的功率范围在5-9kW，功率密度范围在4.17-7.5w/cm 2。
在其中一些实施例中，所述沉积的温度为20-300℃，通过调节温度可实现涂层附着力的变化。
在其中一些实施例中，所述沉积的时间为30-40min，沉积时间对应薄膜厚度，可获得不同厚度的涂层。
本申请上述实施例采用中频溅射的原理，在所述双极板表面形成C-Cr涂层，由于使用孪生靶溅射系统，靶材利用率高有更长的使用寿命，更快的溅射速率，同时可以杜绝靶材中毒现象。且采用中频磁控溅射可得到光滑致密，膜层硬度高，膜厚可线性成长，多弧溅射在靶材上施小电压大电流使材料离子化（带正电颗粒），从而高速击向基片(负电)并沉积，粒子态的靶材与工作气体发生化学反应，晶粒成核并长大，形成致密的C:Cr薄膜。
本申请上述实施例提供的表面改性的燃料电池双极板，以燃料电池的双极板为基材，利用真空溅射镀层技术在所述基材的表面形成均匀的C-Cr涂层，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。
以下结合具体实施例对本申请上述技术方案进行详细说明。
实施例1
1、用清洗机清洗316不锈钢双极板表面，共清洗5次，每次1h20min，在每次清洗间将衬底方向调换，除去表面的灰尘。并在烘箱中用90℃将不锈钢双极板烘烤10分钟，去除水气；
2、将316不锈钢双极板放入超声清洗机，用丙酮进行超声波预清洗，完成后用氮气将表面吹干。然后将双极板放在真空室中的基板支架上，紧接着进行Ar等离子蚀刻10分钟，以去除表面氧化物污染。
3、启动机械泵，当压强小于1kPa时启动罗茨泵，当压强小于17Pa时启动分子泵，将镀膜室内抽真空。将样品置于样品架上，压强达到10-3Pa以下后将样品架传输至加热室内，在腔室内保温30min。(室温条件下样品无需加热)
4、开启高压电源，将功率调节至5kW，短时间内通入大量Ar，进行10min预溅射，同时进行管道清洗。靶面启辉后即可将Ar流量降至工作所需大小。
5、当溅射室气压保持在0.3-0.8Pa时，将样品架传输至溅射室内，调节样品运动速率，启动控制程序，在样品表面制备C:Cr薄膜。以溅射功率5kW，Ar流量500sccm的工作参数在样品表面制备疏松层，以提高表面附着力。再以溅射功率9kW，Ar流量200sccm的参数制备致密层，获得致密的C-Cr涂层。
须注意，在第四步中，可通过通入不同流量的H 2，对表面电阻进行调节，以获得使用所需导电性能的涂层。
6、将样品架传输至加热室内，待样品冷却至120℃以下后，将样品传输至进样室，出样。
7、使用台阶仪、X射线荧光光谱仪、扫描电子显微镜等仪器对样品进行表征，以获得样品表面薄膜的厚度、表面组分、表面形貌等参数，即可确定所得薄膜是否达到使用所需标准。
8、将样品装入标记好的真空袋中，抽真空后进行密封，以达到对样品表面的保护。
本申请上述实施例提供的表面改性的燃料电池双极板及其制备方法，以燃料电池的双极板为基材，利用真空溅射镀层技术在所述基材的表面形成均匀的C-Cr涂层，通过使用Cr元素的掺杂C，克服了不锈钢与C薄膜之间附着力较差，碳的沉积存在一些困难的缺陷，与普通的碳薄膜相比，C-Cr薄膜可以提高涂层的界面电导率和耐蚀性，同时使薄膜获得低残余应力和良好的稳定性，并降低源自涂层缺陷的局部腐蚀的风险。
可以理解，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。
以上仅为本申请的较佳实施例而已，仅具体描述了本申请的技术原理，这些描述只是为了解释本申请的原理，不能以任何方式解释为对本申请保护范围的限制。基于此处解释，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进，及本领域的技术人员不需要付出创造性的劳动即可联想到本申请的其他具体实施方式，均应包含在本申请的保护范围之内。

Claims (12)

  1. 一种表面改性的燃料电池双极板，其特征在于，包括双极板及形成于所述双极板表面的C-Cr涂层。
  2. 如权利要求1所述的表面改性的燃料电池双极板，其特征在于，所述双极板为316不锈钢箔。
  3. 如权利要求1所述的表面改性的燃料电池双极板，其特征在于，所述C-Cr涂层的厚度为800-1000nm。
  4. 一种如权利要求1所述的表面改性的燃料电池双极板的制备方法，其特征在于，包括下述步骤：
    在真空环境中通入工作气体；
    于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶；
    将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上。
  5. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在真空环境中通入工作气体的步骤中，所述工作气体为氩气或氢气与氩气的混合气体。
  6. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在真空环境中通入工作气体的步骤中，具体包括：在镀膜室内抽真空，并通入工作气体，抽真空使得本体压强保持在1*10 ‑ 3Pa以下，通入工作气体后工作压强范围在0.3-0.8Pa。
  7. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶的步骤中，所述靶材和所述双极板的距离在100～150mm。
  8. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在于上述工作气体的环境中，将所述双极板置于阳极架上，并在所述阳极架的平行方向设置阴极架，所述阴极架上设置靶材，所述靶材和所述双极板相对设置，所述靶材为固体C：Cr孪生靶的步骤中，所述靶材的规格为600mm*100mm*5mm，孪生靶材表面积为1200cm 2。
  9. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述高压电源的功率范围在5-9kW，功率密度范围在4.17-7.5W/cm 2。
  10. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述沉积的温度范围为20-300℃。
  11. 如权利要求4所述的表面改性的燃料电池双极板的制备方法，其特征在于，在将所述阴极架接入高压电源，所述高压电源将所述靶材中靶原子激发成粒子态，被激发的粒子沿所述双极板方向运动并沉积在所述双极板上的步骤中，所述沉积的时间为30-40min。
  12. 一种燃料电池，其特征在于，包括权利要求4至11任一项所述表面改性的燃料电池双极板。
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CN110797545A (zh) * 2019-10-11 2020-02-14 浙江锋源氢能科技有限公司 一种金属双极板及其制备方法以及燃料电池
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CN114792819A (zh) * 2022-05-12 2022-07-26 苏州氢澜科技有限公司 一种基于Ti涂层表面改性的燃料电池双极板及其制备方法

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