CN113991123A - Fuel cell metal bipolar plate with anti-corrosion film coating and preparation method thereof - Google Patents

Fuel cell metal bipolar plate with anti-corrosion film coating and preparation method thereof Download PDF

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CN113991123A
CN113991123A CN202111245624.6A CN202111245624A CN113991123A CN 113991123 A CN113991123 A CN 113991123A CN 202111245624 A CN202111245624 A CN 202111245624A CN 113991123 A CN113991123 A CN 113991123A
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layer
corrosion
conductive
ald
bipolar plate
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卓颖
徐一凡
唐厚闻
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Shanghai H Rise New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Vapour Deposition (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to a fuel cell metal bipolar plate with an anti-corrosion film coating and a preparation method thereof, wherein the fuel cell metal bipolar plate comprises a stainless steel substrate, and a passivation layer, a conductive transition layer and a conductive anti-corrosion layer which are deposited on the stainless steel substrate layer by layer; and depositing a metal oxide layer on the stainless steel substrate of the metal bipolar plate by using an atomic layer deposition method to serve as a passivation layer to protect the stainless steel substrate. Subsequently, the conductive anti-corrosion layer is prepared by one or more methods of ALD, PVD, CVD, PECVD, electroplating or vacuum evaporation. Compared with the prior art, the thickness of the conductive anticorrosive layer prepared by the ALD technology is smaller than that prepared by the prior art, so that the anticorrosive performance of the polar plate is improved, the cost is reduced, and the time for preparing the film is shortened.

Description

Fuel cell metal bipolar plate with anti-corrosion film coating and preparation method thereof
Technical Field
The invention relates to the field of fuel cells, in particular to a fuel cell metal bipolar plate with an anti-corrosion film coating and a preparation method thereof.
Background
The anti-corrosion coating of the metal bipolar plate of the fuel cell is limited by the coating process (such as electroplating, PVD and the like) to cause the coating to be not compact enough, and in order to meet the requirement of long-time corrosion resistance, the coating needs to have a certain thickness, for example, a gold coating needs to be primed with another coating below the gold coating, and a carbon coating needs to reach a submicron level. These coatings are either produced at high cost due to their thickness requirements or at lengthy production times due to the thickness.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fuel cell metal bipolar plate with an anti-corrosion film coating and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to protect a fuel cell metal bipolar plate with an anti-corrosion thin film coating, which comprises a stainless steel substrate, and a passivation layer, a conductive transition layer and a conductive anti-corrosion layer which are deposited on the stainless steel substrate layer by layer.
Further, the thickness of the passivation layer is 2-5 nm, the thickness of the conductive transition layer is 10-20 nm, and the thickness of the conductive anticorrosive layer is 8-12 nm.
Further, the passivation layer is a ZnO layer or a TiO layer2Layer, V2O5Layer, HfO2One of the layers.
Further, the conductive transition layer is SnO2One of a layer, an Ir layer, a Pt layer, a Pd layer, an Ag layer, a Ti layer, and a TiN layer.
Further, the conductive anticorrosive layer is an Au layer, a Ti layer and Cr3C2Layer, layer C, CaF2Layer, SrF2Layer, MgF2One of a layer and a ZnF layer.
The second purpose of the invention is to protect a preparation method of the fuel cell metal bipolar plate, which comprises the following steps:
s1: cleaning the surface of a substrate and then placing the substrate into an ALD chamber;
s2: injecting a precursor A1, waiting for the precursor A1 to completely react with the substrate, cleaning an ALD (atomic layer deposition) chamber, injecting a reactant B1, and cleaning the ALD chamber to obtain a passivation layer;
s3: injecting a precursor A2, waiting for the precursor A2 to completely react with the substrate, cleaning an ALD (atomic layer deposition) chamber, injecting a reactant B2, and cleaning the ALD chamber to obtain a conductive transition layer;
s4: and preparing a conductive anticorrosive layer on the conductive transition layer to obtain the fuel cell metal bipolar plate with the anticorrosive film coating.
Further, in S2 to S3, a predetermined deposition thickness is obtained through a plurality of ALD cycles in the reactions between a1 and the substrate, a1 and B1, a2 and the substrate, and a2 and B2.
Further, in S2-S3, when B1 or B2 is a plurality of reactants, the ALD cycle is sequentially performed to obtain a predetermined deposition thickness.
Further, in S4, the method for preparing the conductive anti-corrosion layer on the conductive transition layer is one or more of ALD cycle, PVD, CVD, PECVD, electroplating or vacuum evaporation.
Further, in S2 to S3, the temperature of the ALD chamber is controlled to be 50 ℃ to 500 ℃, the vacuum degree of the chamber is controlled to be 10 Pa to 100Pa, inert gas is used as carrier gas, and the flow rate is controlled to be 30sccm to 300 sccm.
Compared with the prior art, the invention has the following technical advantages:
1. according to the invention, the stainless steel substrate is completely covered by the compact passivation layer with the thickness of about 3nm, so that any part of the stainless steel substrate is not exposed outside, and the corrosion of the stainless steel substrate is prevented.
2. The thickness of the passivation layer is controlled to be about 3nm, so that the bipolar plate still has good conductivity.
3. The invention relates to a 10-20 nm conductive transition layer (SnO)2Ir, Pt, Pd, Ag, Ti) can ensure good conductivity while protecting the bottom passivation layer from being damaged in the subsequent process of preparing the conductive anti-corrosion layer.
4. The fluoride thin film of the present invention can prevent corrosion of HF.
Drawings
FIG. 1 is a schematic cross-sectional view of a metal bipolar plate for a fuel cell according to the present invention;
FIG. 2 is a schematic diagram of an ALD cycle in accordance with the present teachings;
FIG. 3 is a plot of potentiodynamic scans j-E of example 1;
FIG. 4 is a graph of constant potential test j-t of example 1;
FIG. 5 shows the contact resistance change before and after etching in the case of the conventional coating and example 1.
In the figure: 1. the stainless steel substrate, 2, the passivation layer, 3, the conductive transition layer, 4, the conductive anticorrosive coating.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. In the technical scheme, the characteristics of the raw material model, the material name, the connection structure, the control method, the preparation method and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art.
The technical scheme is different from a coating prepared by an atomic layer deposition method proposed by Jiangsu micro-nano science and technology corporation, and four different functional film coatings need to be prepared. Subsequently, the conductive anticorrosive layer is prepared by ALD, PVD, CVD, PECVD, electroplating or vacuum evaporation.
The invention deposits 3nm dense oxide (ZnO, TiO) on a stainless steel substrate by using ALD technology2,V2O5,HfO2) As a passivation layer.
The invention deposits a 10-20 nm conductive transition layer (SnO) on a passivation layer by using an ALD (atomic layer deposition) technology2,Ir,Pt,Pd,Ag,Ti,TiN)。
The invention prepares the conductive anticorrosive layer (Au, Ti, Cr) on the conductive transition layer by PVD, CVD, PECVD, electroplating or vacuum evaporation3C2C); or depositing CaF with the thickness of about 10nm by using ALD method2,SrF2,MgF2ZnF. As shown in fig. 1.
In specific implementation, the surface is cleanedAnd placing the finished stainless steel substrate into an ALD chamber for deposition of a compact passivation layer. Controlling the temperature of an ALD chamber within the range of 50-500 ℃, controlling the vacuum degree of the chamber within the range of 10-100 Pa, and taking inert gas as carrier gas (such as N)2) The flow rate is controlled to be 30 sccm-300 sccm. As shown in FIG. 2, the sample introduction time of the precursor A of the advanced sample is 0.3 s-5 s, and part of the precursor with higher density can be continuously introduced for multiple times. And waiting for the precursor A to completely react with the substrate for 10-45 s. Then wait for 20-90 s to clean the residual unreacted precursor in the chamber. Reactant B was then injected and purged in the same manner. If there are multiple reactants, the remainder is purged in the same manner. As shown in fig. 2, a number of ALD cycles are repeated to obtain the desired deposition thickness.
In specific implementation, a 10-20 nm conductive transition layer is continuously deposited on a sample on which a passivation layer is deposited by using an ALD (atomic layer deposition) technology. Controlling the temperature of an ALD chamber within the range of 50-500 ℃, controlling the vacuum degree of the chamber within the range of 10-100 Pa, and taking inert gas as carrier gas (such as N)2) The flow rate is controlled to be 30 sccm-300 sccm. As shown in fig. 2, a number of ALD cycles are repeated to obtain the desired deposition thickness. SnO2Ir, Pt, Pd, Ag, Ti may be used herein as the conductive transition layer.
In specific implementation, the conductive anticorrosive layer (Au, Ti, Cr)3C2And C) preparing by ALD cycle, PVD, CVD, PECVD, electroplating or vacuum evaporation. Or depositing CaF with the thickness of about 10nm by using ALD method2,SrF2,MgF2。
Example 1
With TTIP (titanium tetraisopropoxide Ti [ OCH (CH))3)2]4) The sample introduction time, the waiting time and the cleaning time of the metal precursor (precursor A) are respectively as follows: 0.5s |15s |30s, water is the reactant of the oxygen source (reactant B), and the sample introduction time, the waiting time and the cleaning time are respectively as follows: 2s |15s |30 s. The temperature of the reaction chamber is controlled at 150 ℃, 20 cycles of ALD are circulated, and TiO with the particle size of about 3nm is obtained2As a passivation layer, the stainless steel substrate is protected.
With TDMASn (tetrakis (dimethylamino) tin [ (CH)3)2N]4Sn) is used as a precursor A,the preheating value of the precursor A is 60 ℃, and the sample introduction time, the waiting time and the cleaning time are respectively as follows: 0.3s |15s |30s, hydrogen peroxide (30% H)2O2) The oxygen source reactant (reactant B) is prepared by the following steps of: 0.5s |15s |30 s. The temperature of the reaction chamber is controlled at 200 ℃, 100 ALD cycles are carried out, and about 20nm SnO is obtained2As a conductive transition layer.
In example 1, about 20nm of Au was deposited by PVD.
Example 1 sample prepared at 80 ℃ H2SO4Potentiodynamic scans were performed on the samples obtained in example 1 from-0.6V to 1.2V vs. she at a sweep rate of 0.1mV/s in an etching solution of +0.1ppm HF (pH 3). As shown in FIG. 3, the corrosion potential of the sample of example 1 was 0.69V, and the corrosion current density at 0.84V was 2.17X 10-7A cm–2。
Example 1 sample prepared at 80 ℃ H2SO4And 0.1ppm HF in an etching solution (pH 3), and a voltage of 0.84V vs. she was applied to perform a potentiostatic test for 200h, and the change in etching current density with time was as shown in fig. 4. The average corrosion current density in the last hour was 5.85X 10-9A cm–2。
The contact resistance before and after the corrosion was compared between the sample obtained in example 1 and the sample of the general coating, as shown in fig. 5. Under the packaging pressure of 60N/cm2In the case of (1), the contact resistance of the sample with the conventional coating after the corrosion test was from the initial 5.46 m.OMEGA.cm2Increased to 14.41 m.OMEGA.cm2On the other hand, the sample of example 1 showed little change in contact resistance after 200 hours of corrosion testing, from the first 3.39m Ω cm2Increased to 5.52 m.OMEGA.cm2. It is thus shown that the coating of example 1 ensures both corrosion resistance and good electrical conductivity.
Example 2
Based on example 1, the technical scheme can be developed that oxides ZnO and TiO are used2，V2O5，HfO2Can be used as a passivation layer to protect the stainless steel substrate. SnO2，Ir，Pt，Pd，Ag，Ti may be used herein as a conductive transition layer. Conductive anti-corrosion layer (Au, Ti, Cr)3C2And C) preparing by ALD cycle, PVD, CVD, PECVD, electroplating or vacuum evaporation. Or depositing CaF with the thickness of about 10nm by using ALD method2，SrF2，MgF2。
The precursors and corresponding reactants required for ALD deposition of each coating in this solution are shown in table 1.
TABLE 1 list of precursors and their corresponding reactants required for the preparation of ALD coatings described in the present invention
Figure BDA0003320853260000051
Figure BDA0003320853260000061
Figure BDA0003320853260000071
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The fuel cell metal bipolar plate with the anti-corrosion thin film coating is characterized by comprising a stainless steel substrate (1), and a passivation layer (2), a conductive transition layer (3) and a conductive anti-corrosion layer (4) which are deposited on the stainless steel substrate (1) layer by layer.
2. The fuel cell metal bipolar plate with the anti-corrosion thin film coating according to claim 1, wherein the passivation layer (2) has a thickness of 2-5 nm, the conductive transition layer (3) has a thickness of 10-20 nm, and the conductive anti-corrosion layer (4) has a thickness of 8-12 nm.
3. The fuel cell metal bipolar plate with a corrosion-resistant thin film coating according to claim 1, characterized in that the passivation layer (2) is a ZnO layer, a TiO layer2Layer, V2O5Layer, HfO2One of the layers.
4. The fuel cell metal bipolar plate with anti-corrosion thin film coating according to claim 1, wherein the conductive transition layer (3) is SnO2One of a layer, an Ir layer, a Pt layer, a Pd layer, an Ag layer, a Ti layer, and a TiN layer.
5. The fuel cell metal bipolar plate with a thin corrosion-resistant coating according to claim 1, wherein the conductive corrosion-resistant layer (4) is an Au layer, a Ti layer, a Cr layer3C2Layer, layer C, CaF2Layer, SrF2Layer, MgF2One of a layer and a ZnF layer.
6. The method of manufacturing a fuel cell metallic bipolar plate as claimed in claim 1, comprising the steps of:
s1: cleaning the surface of a substrate and then placing the substrate into an ALD chamber;
s2: injecting a precursor A1, waiting for the precursor A1 to completely react with the substrate, cleaning an ALD (atomic layer deposition) chamber, injecting a reactant B1, and cleaning the ALD chamber to obtain a passivation layer;
s3: injecting a precursor A2, waiting for the precursor A2 to completely react with the substrate, cleaning an ALD (atomic layer deposition) chamber, injecting a reactant B2, and cleaning the ALD chamber to obtain a conductive transition layer;
s4: and preparing a conductive anticorrosive layer on the conductive transition layer to obtain the fuel cell metal bipolar plate with the anticorrosive film coating.
7. The method of claim 6, wherein the predetermined deposition thickness is obtained by a plurality of ALD cycles in the reactions between A1 and the substrate, A1 and B1, A2 and the substrate, and A2 and B2 in S2 to S3.
8. The method as claimed in claim 6, wherein the predetermined deposition thickness is obtained by sequentially performing ALD cycles when B1 or B2 is a plurality of reactants from S2 to S3.
9. The method of claim 6, wherein the conductive corrosion protection layer is formed on the conductive transition layer by one or more of ALD cycle, PVD, CVD, PECVD, electroplating or vacuum evaporation in S4.
10. The method as claimed in claim 6, wherein in S2 to S3, the temperature of the ALD chamber is controlled to 50 ℃ to 500 ℃, the vacuum degree of the chamber is controlled to 10 Pa to 100Pa, inert gas is used as carrier gas, and the flow rate is controlled to 30sccm to 300 sccm.
CN202111245624.6A 2021-10-26 2021-10-26 Fuel cell metal bipolar plate with anti-corrosion film coating and preparation method thereof Pending CN113991123A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011987A (en) * 2022-08-02 2022-09-06 中国华能集团清洁能源技术研究院有限公司 Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof
CN115418611A (en) * 2022-08-16 2022-12-02 浙江天能氢能源科技有限公司 Preparation method of gold-plated coating of metal bipolar plate of fuel cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011987A (en) * 2022-08-02 2022-09-06 中国华能集团清洁能源技术研究院有限公司 Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof
CN115418611A (en) * 2022-08-16 2022-12-02 浙江天能氢能源科技有限公司 Preparation method of gold-plated coating of metal bipolar plate of fuel cell

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