CN109023282A - A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces - Google Patents
A kind of preparation method preparing CrMoTiN nitride film nano coating in bipolar plate surfaces Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002103 nanocoating Substances 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000005498 polishing Methods 0.000 claims abstract description 13
- 229910000619 316 stainless steel Inorganic materials 0.000 claims abstract description 10
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 7
- 239000010432 diamond Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 7
- 244000137852 Petrea volubilis Species 0.000 claims 2
- 239000006071 cream Substances 0.000 claims 2
- 239000011521 glass Substances 0.000 claims 2
- 238000004062 sedimentation Methods 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 1
- 238000005520 cutting process Methods 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 5
- 238000007733 ion plating Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000005240 physical vapour deposition Methods 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 description 8
- 230000010287 polarization Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 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
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- 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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- 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
- C23C14/0641—Nitrides
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- 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
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- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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Abstract
一种在双极板表面制备CrMoTiN氮化膜纳米涂层的制备方法，包括以下步骤：1)用SiC砂纸分别对316不锈钢双极板基体进行打磨，然后用金刚石抛光膏对研磨的基体抛光到镜面程度；2)在镀膜之前，去除表面油污，得到预处理基体；3)将预处理基体放入真空室腔体内，利用非平衡磁控溅射离子镀技术在其表面沉积四元氮化膜CrMoTiN来对不锈钢基体进行表面改性。本发明利用物理气相沉积技术在CrMoN涂层表面改性的双极板的基础上添加Ti元素，提供一种新的四元氮化物CrMoTiN涂层，通过Mo、Ti等元素参杂，进一步提高双极板材料的耐蚀性和保证导电性。A preparation method for preparing CrMoTiN nitride film nano-coating on the surface of a bipolar plate, comprising the following steps: 1) grinding the 316 stainless steel bipolar plate substrate with SiC sandpaper, then polishing the ground substrate with diamond polishing paste to Mirror level; 2) Before coating, remove the surface oil to obtain a pretreated substrate; 3) Put the pretreated substrate into the vacuum chamber cavity, and use unbalanced magnetron sputtering ion plating technology to deposit quaternary nitride film on its surface CrMoTiN is used for surface modification of stainless steel substrates. The present invention uses physical vapor deposition technology to add Ti element on the basis of CrMoN coating surface modified bipolar plate, provides a new quaternary nitride CrMoTiN coating, and further improves bipolar plate by doping Mo, Ti and other elements. Corrosion resistance of the plate material and ensure electrical conductivity.
Description
技术领域technical field
本发明涉及一种质子交换膜燃料电池双极板材料上涂层的制备方法，即通过闭合场非平衡磁控溅射技术在双极板表面沉积CrMoTiN四元氮化膜来提高燃料电池双极板的耐蚀性和导电率，保证电池使用的可靠性能及延长使用寿命。The invention relates to a method for preparing a coating on a bipolar plate material of a proton exchange membrane fuel cell, that is, a CrMoTiN quaternary nitride film is deposited on the surface of the bipolar plate by closed-field unbalanced magnetron sputtering technology to improve the bipolar properties of the fuel cell. The corrosion resistance and conductivity of the plate ensure the reliable performance of the battery and prolong the service life.
背景技术Background technique
质子交换膜燃料电池不但能量转换率高、环境友好，而且可以在室温快速启动、无电解流失、寿命长、比功率和比能量高。特别适合用来作为可移动动力源，是电动车和分散电站的理想电源之一，在替代传统化石能源方面有广泛的应用前景。Proton exchange membrane fuel cells not only have high energy conversion rate and are environmentally friendly, but also can start quickly at room temperature, have no electrolytic loss, have long life, and have high specific power and specific energy. It is especially suitable for use as a mobile power source, and is one of the ideal power sources for electric vehicles and decentralized power stations, and has broad application prospects in replacing traditional fossil energy.
双极板是燃料电池的重要组件之一，它占电池堆总体积的80％、质量的70％，以及成本的30％。它具有集流、散热、均匀分散反应介质以及冷却作用，同时具有支撑膜电极、隔绝反应气体以及密封性的要求。所以理想的双极板材料应该具有良好的导电性、高气密性、高的机械强度、以及易于加工等特点。石墨及其复合物具有良好的导电性，易于加工，但是材料脆性大、机械性能差、加工成本较高，不利于大规模的商业应用。金属双极板材料具有高的机械强度、良好的导电性、易于加工、成本较低，可以大规模商用。然而在酸性的质子交换膜燃料电池环境中，金属双极板材料易被腐蚀，形成钝化膜，增大双极板与气体扩散膜之间的接触电阻，同时污染膜电极，损害电池堆。所以需要对不锈钢双极板进行表面改性来提高耐蚀性、导电性。The bipolar plate is one of the important components of the fuel cell, which accounts for 80% of the total volume of the cell stack, 70% of the mass, and 30% of the cost. It has the functions of current collection, heat dissipation, uniform dispersion of reaction medium and cooling, and at the same time has the requirements of supporting membrane electrodes, isolating reaction gas and sealing. Therefore, the ideal bipolar plate material should have good electrical conductivity, high air tightness, high mechanical strength, and easy processing. Graphite and its composites have good electrical conductivity and are easy to process, but the materials are brittle, have poor mechanical properties, and high processing costs, which are not conducive to large-scale commercial applications. Metal bipolar plate materials have high mechanical strength, good electrical conductivity, easy processing, low cost, and can be commercially used on a large scale. However, in the acidic proton exchange membrane fuel cell environment, the metal bipolar plate material is easily corroded, forming a passivation film, increasing the contact resistance between the bipolar plate and the gas diffusion membrane, contaminating the membrane electrodes, and damaging the battery stack. Therefore, it is necessary to modify the surface of the stainless steel bipolar plate to improve the corrosion resistance and conductivity.
发明内容Contents of the invention
为了克服已有双极板材料的耐腐蚀性较低和导电性较差的不足，本发明提供了一种在双极板表面制备CrMoTiN氮化膜纳米涂层的制备方法，利用物理气相沉积技术在CrMoN涂层表面改性的双极板的基础上添加Ti元素，提供一种新的四元氮化物CrMoTiN涂层,通过Mo、Ti等元素参杂，进一步提高双极板材料的耐蚀性和保证导电性。In order to overcome the shortcomings of the existing bipolar plate materials with low corrosion resistance and poor electrical conductivity, the invention provides a method for preparing a CrMoTiN nitride film nano-coating on the surface of the bipolar plate, using physical vapor deposition technology Adding Ti element on the basis of the CrMoN coating surface modified bipolar plate provides a new quaternary nitride CrMoTiN coating, and further improves the corrosion resistance of the bipolar plate material by doping Mo, Ti and other elements and ensure electrical conductivity.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve its technical problems is:
一种在双极板表面制备CrMoTiN氮化膜纳米涂层的制备方法，所述制备方法包括以下步骤：A preparation method for preparing a CrMoTiN nitride film nano-coating on the surface of a bipolar plate, the preparation method comprising the following steps:
1)用SiC砂纸分别对316不锈钢双极板基体进行打磨，然后用金刚石抛光膏对研磨的基体抛光到镜面程度；1) Grinding the 316 stainless steel bipolar plate substrates with SiC sandpaper, and then polishing the ground substrates to a mirror surface with diamond polishing paste;
2)在镀膜之前，去除表面油污，得到预处理基体；2) Before coating, remove surface oil stains to obtain a pretreated substrate;
3)将预处理基体放入真空室腔体内，关闭真空室门，抽真空至预设阈值，腔体中有两块对称放置的高纯Cr靶、一块高纯Mo靶以及一块高纯Ti靶，氩气作为保护性气体运行镀膜程序；3) Put the pretreated substrate into the vacuum chamber cavity, close the vacuum chamber door, and evacuate to the preset threshold. There are two symmetrically placed high-purity Cr targets, one high-purity Mo target and one high-purity Ti target in the cavity , Argon is used as a protective gas to run the coating process;
在-520V～-480V偏压和所有靶电流都设置为0.2～0.4A的情况下，离子溅射轰击预处理基体表面25～35min；In the case of -520V ~ -480V bias and all target currents are set to 0.2 ~ 0.4A, ion sputtering bombards the surface of the pretreated substrate for 25 ~ 35min;
Cr靶电流提升至3～5A，Mo靶和Ti靶电流相应微小提升至0.4～0.6A，沉积3～8min得到Cr过渡层以增加膜基结合力；The Cr target current is increased to 3-5A, and the Mo target and Ti target current are slightly increased to 0.4-0.6A, and the Cr transition layer is obtained by depositing for 3-8 minutes to increase the bonding force of the film base;
通入氮气作为反应气体在Cr层表面沉积10～20min，得到CrN膜；Introduce nitrogen gas as a reaction gas to deposit on the surface of the Cr layer for 10-20 minutes to obtain a CrN film;
调节Mo靶电流至3～5A，沉积10～20min，得到CrMoN膜；Adjust the Mo target current to 3-5A, deposit for 10-20min, and obtain CrMoN film;
最后沉积CrMoTiN膜，Ti靶电流范围为0.3A-6A，沉积时间为40～80min，以得到含Ti的CrMoTiN涂层。Finally, the CrMoTiN film is deposited, the Ti target current range is 0.3A-6A, and the deposition time is 40-80min, so as to obtain the Ti-containing CrMoTiN coating.
进一步，所述步骤3)中，所述预设阈值为2.5×10-5torr；在-500V偏压和所有靶电流都设置为0.3A的情况下，离子溅射轰击基体表面30min，Cr靶电流提升至4A，Mo靶和Ti靶电流相应微小提升至0.5A，沉积5min得到Cr过渡层，通入氮气作为反应气体在Cr层表面沉积15min，得到CrN膜；调节Mo靶电流至4A，沉积15min，得到CrMoN膜；最后沉积CrMoTiN膜，Ti靶电流范围为0.3A-6A，沉积时间为60min，以得到含Ti的CrMoTiN涂层。Further, in the step 3), the preset threshold value is 2.5×10 -5 torr; under the condition that the bias voltage of -500V and all target currents are set to 0.3A, the ion sputtering bombards the surface of the substrate for 30min, and the Cr target The current is increased to 4A, and the Mo target and Ti target currents are slightly increased to 0.5A, and the Cr transition layer is obtained by depositing for 5 minutes. Nitrogen is introduced as a reaction gas to deposit on the surface of the Cr layer for 15 minutes to obtain a CrN film; adjust the Mo target current to 4A, and deposit 15 minutes to obtain a CrMoN film; finally deposit a CrMoTiN film, the Ti target current ranges from 0.3A to 6A, and the deposition time is 60 minutes to obtain a Ti-containing CrMoTiN coating.
再进一步，所述步骤1)中，对316不锈钢棒材线切割，加工至设定尺寸得到双极板基体，用粒度为400#、800#、1200#、1500#、2000#的SiC砂纸分别对基体进行打磨，然后用粒度为0.1μm的金刚石抛光膏对研磨的基体抛光到镜面程度。Further, in the step 1), wire-cut the 316 stainless steel bar, process it to the set size to obtain the bipolar plate substrate, and use SiC sandpaper with a particle size of 400#, 800#, 1200#, 1500#, 2000# respectively The substrate is ground, and then the ground substrate is polished to a mirror surface with a diamond polishing paste with a particle size of 0.1 μm.
更进一步，所述步骤2)中，用超声设备把抛光基体分别放入丙酮、无水乙醇、去离子水中超声15～25min。Furthermore, in the step 2), ultrasonic equipment is used to put the polishing substrate into acetone, absolute ethanol, and deionized water respectively for 15-25 minutes.
本发明中，物理气相沉积技术制备所得的涂层纯度高、致密性好、涂层与基体结合力高，涂层性能不受基体材料的影响，是比较理想的双极板表面改性技术，而且尤以氮化物涂层制备居多。但是物理气相沉积技术制备的单一氮化物涂层存在的缺陷会形成原电池，导致局部腐蚀。通过沉积复合膜和添加额外元素的方式可以有效地避免这个问题的出现。闭合场非平衡磁控溅射离子镀设备结合了磁控溅射技术和离子镀技术的优点，膜层厚度均匀，涂层与基体之间具由较高的结合力，同时具有很高的灵活性，可以用来制备梯度膜涂层和在同一基体上沉积多层涂层。In the present invention, the coating prepared by physical vapor deposition technology has high purity, good compactness, high bonding force between the coating and the substrate, and the coating performance is not affected by the substrate material, which is an ideal bipolar plate surface modification technology. And especially the nitride coating is mostly prepared. However, defects in the single nitride coating prepared by physical vapor deposition technology can form galvanic cells, resulting in localized corrosion. This problem can be effectively avoided by depositing composite films and adding additional elements. The closed field unbalanced magnetron sputtering ion plating equipment combines the advantages of magnetron sputtering technology and ion plating technology, the film thickness is uniform, the coating and the substrate have a high bonding force, and it has high flexibility. It can be used to prepare gradient film coatings and deposit multi-layer coatings on the same substrate.
本发明的有益效果主要表现在：通过三电极系统对其进行包括动极化测试、稳态极化测试以及电化学阻抗谱的电化学测试，模拟PEMFCs使用环境，测试结果表明：新的四元氮化物CrMoTiN涂层表面改性双极板相对316不锈钢基体腐蚀电位有很大提升，腐蚀电流密度下降了两个数量级；比CrTiN涂层耐腐蚀性能提高一倍以上。膜基结合力大约46N。The beneficial effect of the present invention is mainly manifested in: the electrochemical test including dynamic polarization test, steady state polarization test and electrochemical impedance spectroscopy is carried out through the three-electrode system, and the use environment of PEMFCs is simulated. The test results show that: the new quaternary Compared with the 316 stainless steel substrate, the corrosion potential of the nitride CrMoTiN coating surface modified bipolar plate is greatly improved, and the corrosion current density is reduced by two orders of magnitude; the corrosion resistance of the CrTiN coating is more than double that of the CrTiN coating. The binding force of membrane base is about 46N.
具体实施方式Detailed ways
下面对本发明作进一步描述。The present invention will be further described below.
一种在双极板表面制备CrMoTiN氮化膜纳米涂层的制备方法，所述制备方法包括以下步骤：A preparation method for preparing a CrMoTiN nitride film nano-coating on the surface of a bipolar plate, the preparation method comprising the following steps:
1)用SiC砂纸分别对316不锈钢双极板基体进行打磨，然后用金刚石抛光膏对研磨的基体抛光到镜面程度；1) Grinding the 316 stainless steel bipolar plate substrates with SiC sandpaper, and then polishing the ground substrates to a mirror surface with diamond polishing paste;
2)在镀膜之前，去除表面油污，得到预处理基体；2) Before coating, remove surface oil stains to obtain a pretreated substrate;
3)将预处理基体放入真空室腔体内，关闭真空室门，抽真空至预设阈值，腔体中有两块对称放置的高纯Cr靶、一块高纯Mo靶以及一块高纯Ti靶，氩气作为保护性气体运行镀膜程序；3) Put the pretreated substrate into the vacuum chamber cavity, close the vacuum chamber door, and evacuate to the preset threshold. There are two symmetrically placed high-purity Cr targets, one high-purity Mo target and one high-purity Ti target in the cavity , Argon is used as a protective gas to run the coating process;
在-520V～-480V偏压和所有靶电流都设置为0.2～0.4A的情况下，离子溅射轰击预处理基体表面25～35min；In the case of -520V ~ -480V bias and all target currents are set to 0.2 ~ 0.4A, ion sputtering bombards the surface of the pretreated substrate for 25 ~ 35min;
Cr靶电流提升至3～5A，Mo靶和Ti靶电流相应微小提升至0.4～0.6A，沉积3～8min得到Cr过渡层以增加膜基结合力；The Cr target current is increased to 3-5A, and the Mo target and Ti target current are slightly increased to 0.4-0.6A, and the Cr transition layer is obtained by depositing for 3-8 minutes to increase the bonding force of the film base;
通入氮气作为反应气体在Cr层表面沉积10～20min，得到CrN膜；Introduce nitrogen gas as a reaction gas to deposit on the surface of the Cr layer for 10-20 minutes to obtain a CrN film;
调节Mo靶电流至3～5A，沉积10～20min，得到CrMoN膜；Adjust the Mo target current to 3-5A, deposit for 10-20min, and obtain CrMoN film;
最后沉积CrMoTiN膜，Ti靶电流范围为0.3A-6A，沉积时间为40～80min，以得到含Ti的CrMoTiN涂层。Finally, the CrMoTiN film is deposited, the Ti target current range is 0.3A-6A, and the deposition time is 40-80min, so as to obtain the Ti-containing CrMoTiN coating.
进一步，所述步骤3)中，所述预设阈值为2.5×10-5torr；在-500V偏压和所有靶电流都设置为0.3A的情况下，离子溅射轰击基体表面30min，Cr靶电流提升至4A，Mo靶和Ti靶电流相应微小提升至0.5A，沉积5min得到Cr过渡层，通入氮气作为反应气体在Cr层表面沉积15min，得到CrN膜；调节Mo靶电流至4A，沉积15min，得到CrMoN膜；最后沉积CrMoTiN膜，Ti靶电流范围为0.3A-6A，沉积时间为60min，以得到含Ti的CrMoTiN涂层。Further, in the step 3), the preset threshold value is 2.5×10 -5 torr; under the condition that the bias voltage of -500V and all target currents are set to 0.3A, the ion sputtering bombards the surface of the substrate for 30min, and the Cr target The current is increased to 4A, and the Mo target and Ti target currents are slightly increased to 0.5A, and the Cr transition layer is obtained by depositing for 5 minutes. Nitrogen is introduced as a reaction gas to deposit on the surface of the Cr layer for 15 minutes to obtain a CrN film; adjust the Mo target current to 4A, and deposit 15 minutes to obtain a CrMoN film; finally deposit a CrMoTiN film, the Ti target current ranges from 0.3A to 6A, and the deposition time is 60 minutes to obtain a Ti-containing CrMoTiN coating.
再进一步，所述步骤1)中，对316不锈钢棒材线切割，加工至设定尺寸得到双极板基体，用粒度为400#、800#、1200#、1500#、2000#的SiC砂纸分别对基体进行打磨，然后用粒度为0.1μm的金刚石抛光膏对研磨的基体抛光到镜面程度。Further, in the step 1), wire-cut the 316 stainless steel bar, process it to the set size to obtain the bipolar plate substrate, and use SiC sandpaper with a particle size of 400#, 800#, 1200#, 1500#, 2000# respectively The substrate is ground, and then the ground substrate is polished to a mirror surface with a diamond polishing paste with a particle size of 0.1 μm.
更进一步，所述步骤2)中，用超声设备把抛光基体分别放入丙酮、无水乙醇、去离子水中超声15～25min。Furthermore, in the step 2), ultrasonic equipment is used to put the polishing substrate into acetone, absolute ethanol, and deionized water respectively for 15-25 minutes.
本发明提供一种316不锈钢制备的双极板及其表面改性层。即以316不锈钢为基体，利用非平衡磁控溅射离子镀技术在其表面沉积四元氮化膜CrMoTiN来对不锈钢基体进行表面改性，并通过动电位极化测试来表征表面改性膜的耐蚀性。模拟PEMFCs使用环境，测试结果表明：新的四元氮化物CrMoTiN涂层表面改性双极板相对316不锈钢基体腐蚀电位有很大提升，腐蚀电流密度下降了两个数量级；比CrTiN涂层耐腐蚀性能提高一倍以上。膜基结合力大约46N。The invention provides a bipolar plate made of 316 stainless steel and a surface modification layer thereof. That is, 316 stainless steel is used as the substrate, and the quaternary nitride film CrMoTiN is deposited on the surface by unbalanced magnetron sputtering ion plating technology to modify the surface of the stainless steel substrate, and the surface modification film is characterized by the dynamic potential polarization test. Corrosion resistance. The test results show that the new quaternary nitride CrMoTiN coating surface modified bipolar plate has greatly improved the corrosion potential of the 316 stainless steel substrate, and the corrosion current density has dropped by two orders of magnitude; the corrosion resistance of the CrTiN coating is higher than that of the CrTiN coating. Performance is more than doubled. The binding force of membrane base is about 46N.
实施例1Example 1
将预处理基体放入真空室腔体内，关闭真空室门，抽真空至2.5×10-5torr。腔体中有两块对称放置的高纯Cr靶、一块高纯Mo靶以及一块高纯Ti靶。氩气作为保护性气体运行镀膜程序。在-520V偏压和所有靶电流都设置为0.2A的情况下，离子溅射轰击基体表面25min，已达到去除表面氧化膜和杂质的目的。Cr靶电流提升至3A，Mo靶和Ti靶电流相应微小提升至0.4A，沉积3min得到Cr过渡层以增加膜基结合力。通入氮气作为反应气体在Cr层表面沉积10min，得到CrN膜。调节Mo靶电流至3A，沉积10min，得到CrMoN膜。Ti靶电流仍然维持在0.3A，继续沉积40min，完成镀膜工艺，待冷却，取出试样。Put the pretreated substrate into the vacuum chamber cavity, close the vacuum chamber door, and evacuate to 2.5×10 -5 torr. There are two symmetrically placed high-purity Cr targets, one high-purity Mo target and one high-purity Ti target in the cavity. Argon is used as protective gas to run the coating process. Under the condition of -520V bias and all target currents set to 0.2A, ion sputtering bombarded the surface of the substrate for 25min, which has achieved the purpose of removing the surface oxide film and impurities. The Cr target current was increased to 3A, and the Mo target and Ti target current were slightly increased to 0.4A, and the Cr transition layer was deposited for 3 minutes to increase the bonding force of the film base. Nitrogen gas was introduced as a reaction gas to deposit on the surface of the Cr layer for 10 minutes to obtain a CrN film. Adjust the Mo target current to 3A, and deposit for 10 minutes to obtain a CrMoN film. The Ti target current is still maintained at 0.3A, and the deposition is continued for 40 minutes to complete the coating process. After cooling, the sample is taken out.
本实例制备所得的CrMoTiN复合膜双极板动电位极化测试的腐蚀电流密度为2.62×10-7A cm-2，在1.5MPa时，涂层与碳纸之间的界面接触电阻为6.2mΩcm2。The corrosion current density of the CrMoTiN composite film bipolar plate prepared in this example is 2.62×10 -7 A cm -2 in the potentiodynamic polarization test. At 1.5 MPa, the interface contact resistance between the coating and the carbon paper is 6.2 mΩcm 2 .
实施例2Example 2
将预处理基体放入真空室腔体内，关闭真空室门，抽真空至2.5×10-5torr。腔体中有两块对称放置的高纯Cr靶、一块高纯Mo靶以及一块高纯Ti靶。氩气作为保护性气体运行镀膜程序。在-500V偏压和所有靶电流都设置为0.3A的情况下，离子溅射轰击基体表面30min，已达到去除表面氧化膜和杂质的目的。Cr靶电流提升至4A，Mo靶和Ti靶电流相应微小提升至0.5A，沉积5min得到Cr过渡层以增加膜基结合力。通入氮气作为反应气体在Cr层表面沉积15min，得到CrN膜。调节Mo靶电流至4A，沉积15min，得到CrMoN膜。最后沉积CrMoTiN膜，Ti靶电流升到2A，沉积时间为60min。Put the pretreated substrate into the vacuum chamber cavity, close the vacuum chamber door, and evacuate to 2.5×10 -5 torr. There are two symmetrically placed high-purity Cr targets, one high-purity Mo target and one high-purity Ti target in the cavity. Argon is used as protective gas to run the coating process. Under the condition of -500V bias and all target currents set to 0.3A, ion sputtering bombarded the surface of the substrate for 30min, and the purpose of removing the surface oxide film and impurities has been achieved. The Cr target current was increased to 4A, and the Mo target and Ti target current were slightly increased to 0.5A, and the Cr transition layer was deposited for 5 minutes to increase the bonding force of the film base. Nitrogen gas was introduced as a reaction gas to deposit on the surface of the Cr layer for 15 minutes to obtain a CrN film. Adjust the Mo target current to 4A, and deposit for 15 minutes to obtain a CrMoN film. Finally, the CrMoTiN film was deposited, the Ti target current was increased to 2A, and the deposition time was 60 minutes.
本实例制备所得的CrMoTiN复合膜双极板动电位极化测试的腐蚀电流密度为1.170×10-7A cm-2，在1.5MPa的压强下，涂层与碳纸之间的界面接触电阻为5.8mΩcm2。The corrosion current density of the CrMoTiN composite film bipolar plate prepared in this example is 1.170×10 -7 A cm -2 in the potentiodynamic polarization test. Under the pressure of 1.5 MPa, the interface contact resistance between the coating and the carbon paper is 5.8 mΩcm 2 .
实施例3Example 3
将预处理基体放入真空室腔体内，关闭真空室门，抽真空至2.5×10-5torr。腔体中有两块对称放置的高纯Cr靶、一块高纯Mo靶以及一块高纯Ti靶。氩气作为保护性气体运行镀膜程序。在-480V偏压和所有靶电流都设置为0.4A的情况下，离子溅射轰击基体表面35min，已达到去除表面氧化膜和杂质的目的。Cr靶电流提升至5A，Mo靶和Ti靶电流相应微小提升至0.6A，沉积8min得到Cr过渡层以增加膜基结合力。通入氮气作为反应气体在Cr层表面沉积20min，得到CrN膜。调节Mo靶电流至5A，沉积20min，得到CrMoN膜。最后沉积CrMoTiN膜，Ti靶电流为6A，沉积时间为80min。Put the pretreated substrate into the vacuum chamber cavity, close the vacuum chamber door, and evacuate to 2.5×10 -5 torr. There are two symmetrically placed high-purity Cr targets, one high-purity Mo target and one high-purity Ti target in the cavity. Argon is used as protective gas to run the coating process. Under the condition of -480V bias and all target currents set to 0.4A, ion sputtering bombarded the surface of the substrate for 35min, and the purpose of removing the surface oxide film and impurities has been achieved. The Cr target current was increased to 5A, and the Mo target and Ti target current were slightly increased to 0.6A, and the Cr transition layer was deposited for 8 minutes to increase the bonding force of the film base. Nitrogen gas was introduced as a reaction gas to deposit on the surface of the Cr layer for 20 minutes to obtain a CrN film. Adjust the Mo target current to 5A, and deposit for 20 minutes to obtain a CrMoN film. Finally, the CrMoTiN film is deposited, the Ti target current is 6A, and the deposition time is 80min.
本实例制备所得的CrMoTiN复合膜双极板动电位极化测试的腐蚀电流密度为5.884×10-8A cm2，在1.5MPa的压强下，涂层与碳纸之间的界面接触电阻为5.2mΩcm2。The corrosion current density of the CrMoTiN composite film bipolar plate prepared in this example was 5.884×10 -8 A cm 2 in the potentiodynamic polarization test. Under the pressure of 1.5 MPa, the interface contact resistance between the coating and the carbon paper was 5.2 mΩcm 2 .
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