CN115354297B - Titanium-based coating fuel cell metal polar plate and preparation method thereof - Google Patents

Titanium-based coating fuel cell metal polar plate and preparation method thereof Download PDF

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Publication number
CN115354297B
CN115354297B CN202210936747.2A CN202210936747A CN115354297B CN 115354297 B CN115354297 B CN 115354297B CN 202210936747 A CN202210936747 A CN 202210936747A CN 115354297 B CN115354297 B CN 115354297B
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polar plate
titanium
titanium alloy
fuel cell
plate substrate
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CN115354297A (en
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杨骄
袁鹏
高鹏然
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Shenzhen Center Power Tech Co Ltd
Shenzhen Hydrogen Fuel Cell Technology Co Ltd
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Shenzhen Center Power Tech Co Ltd
Shenzhen Hydrogen Fuel Cell Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26Deposition of carbon only
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10Oxidising
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0206Metals or alloys
    • H01M8/0208Alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0213Gas-impermeable carbon-containing materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0223Composites
    • H01M8/0228Composites in the form of layered or coated products
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The application discloses a titanium-based coating fuel cell metal polar plate and a preparation method thereof, wherein the preparation method comprises the following steps: s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix; s02, heating the pretreated titanium alloy polar plate substrate, and then introducing oxygen to react for 0.1-2.0 h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer; s03, introducing carbon source gas into the titanium alloy polar plate substrate covered with the titanium oxide transition layer on the surface, heating and then carrying out carbon deposition reaction for 1-100 min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface; s04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, and heating and reacting for 1-100 min to obtain the titanium-based coated fuel cell metal polar plate. The method is simple, low in cost, high in production efficiency and easy for mass production.

Description

Titanium-based coating fuel cell metal polar plate and preparation method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to a titanium-based coating fuel cell metal polar plate and a preparation method thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy in fuel into electric energy through an electrochemical reaction. Compared with the traditional energy source, the fuel cell is an efficient and clean electrochemical power generation device, and has recently received widespread attention at home and abroad.
The bipolar plate is one of the core components of a Proton Exchange Membrane Fuel Cell (PEMFC), and the quality of the bipolar plate directly determines the output power of the cell stack and the service life of the cell stack. The metal bipolar plate is a focus of attention in the current PEMFC bipolar plate research because of excellent mechanical property and electric conductivity. However, the pure metal bipolar plate is easy to corrode in the proton exchange membrane fuel cell environment, and after the metal bipolar plate corrodes, metal ions which can poison a catalyst are released, or a compact oxide film which can increase interface contact resistance is formed, so that the output power and the service life of the fuel cell are greatly influenced.
Disclosure of Invention
Based on the above, the invention provides a titanium-based coated fuel cell metal polar plate and a preparation method thereof, which aim to solve the problems that the existing metal polar plate is easy to corrode in a proton exchange membrane fuel cell environment, and after the metal polar plate corrodes, metal ions which can poison a catalyst are released, or a compact oxide film which can increase interface contact resistance is formed, so that the output power and the service life of the fuel cell are greatly influenced, and the like. The compact titanium carbide layer is prepared on the surface of the titanium alloy matrix, so that the effects of enhancing conductivity, corrosion resistance and mechanical property are achieved, and the high-performance and long-time use requirements of the fuel cell metal polar plate are met.
In order to achieve the above object, in one aspect, the embodiment of the present invention provides a method for preparing a metal electrode plate of a titanium-based coated fuel cell, including the steps of:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 300-600 ℃, and then introducing oxygen to react for 0.1-2.0 h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800-1000 ℃, and then carrying out carbon deposition reaction for 1-100 min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer with carbon deposited on the surface;
s04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200-1500 ℃ and reacting for 1-100 min to obtain the titanium-based coated fuel cell metal polar plate.
In a preferred embodiment, in step S01,
the thickness of the titanium alloy polar plate substrate is preferably 0.01-10 mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.001 mm-0.1 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In a preferred embodiment, in step S02,
the heating rate is preferably 10 to 50 ℃/min.
The flow rate of the oxygen gas is preferably 10sccm to 100sccm.
In a preferred embodiment, in step S03,
the carbon source gas is preferably CH 4 、C 2 H 2 CO or C 2 H 4 And (3) waiting for gas.
The flow rate of the carbon source gas is preferably 10sccm to 100sccm.
The heating rate is preferably 10 to 50 ℃/min.
In a preferred embodiment, in step S04,
the rare gas is preferably argon.
The flow rate of the rare gas is 50sccm to 200sccm.
The heating rate is preferably 10 to 50 ℃/min.
On the other hand, the embodiment of the application also provides the titanium-based coating fuel cell metal polar plate obtained by the preparation method.
According to the method, a layer of compact titanium carbide is prepared on the surface of the titanium alloy substrate, so that the effects of enhancing the conductivity, corrosion resistance and mechanical property of the metal electrode plate of the fuel cell are achieved, the high-performance and long-time use requirements of the metal electrode plate of the fuel cell are met, and the problems that the existing metal electrode plate is easy to corrode in a proton exchange membrane fuel cell environment, metal ions capable of poisoning a catalyst are released after the metal electrode plate corrodes, or a compact oxide film capable of increasing interface contact resistance is formed, the output power and the service life of the fuel cell are greatly influenced and the like can be solved. The preparation method disclosed by the invention is simple, is more environment-friendly, has lower production cost and higher production efficiency, and is easy for batch or large-scale production.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the embodiments.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications (such as up, down, left, right, front, back, top, bottom … …) are included in the embodiments of the present invention, the directional indications are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture, and if the specific posture is changed, the directional indications are correspondingly changed.
In this application, unless specifically stated and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art as the case may be.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
At present, the existing metal polar plate is easy to corrode in the proton exchange membrane fuel cell environment, and after the metal polar plate corrodes, metal ions which can poison a catalyst are released, or a compact oxide film which can increase interface contact resistance is formed, so that the output power and the service life of the fuel cell are greatly influenced. Based on the foregoing, there is a need for a titanium-based coated fuel cell metal plate and a method for preparing the same to solve the above-mentioned technical problems.
In order to achieve the above object, in one aspect, the embodiment of the present invention provides a method for preparing a metal electrode plate of a titanium-based coated fuel cell, including the steps of:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 300-600 ℃, and then introducing oxygen to react for 0.1-2.0 h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800-1000 ℃, and then carrying out carbon deposition reaction for 1-100 min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer with carbon deposited on the surface;
s04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200-1500 ℃ and reacting for 1-100 min to obtain the titanium-based coated fuel cell metal polar plate.
In the embodiment of the application, the operation of each step can be coordinated maximally by controlling the reaction conditions (including the reaction temperature, the reaction time, the dosage of each reactant and the like) of each step, so that the effect of preparing the titanium-based coated fuel cell metal electrode plate is optimal, the quality of the titanium-based coating is improved while the generation of byproducts is effectively prevented, the uniformity of the coating is ensured, and the stability of the performance of the titanium-based coated fuel cell metal electrode plate is further ensured.
Titanium directly reacts with carbon source gas, the reaction temperature is too high, the reaction condition is harsh, industrialization is difficult, the influence on the base material is relatively large, and the uniformity of the coating is difficult to ensure.
The titanium oxide exists on the surface of the titanium alloy matrix, the titanium oxide transition layer is generated by reacting the matrix with oxygen, then carbon deposition is carried out by reducing carbon source gas, and finally titanium carbide is generated by reacting deposited carbon and titanium oxide, so that the method has mild reaction conditions, is easy to industrialize, can ensure the uniformity of a coating, has higher quality of the coating, and simultaneously ensures that the metal polar plate of the titanium-based coating fuel cell has better stability.
In a preferred embodiment, in step S01,
the thickness of the titanium alloy polar plate substrate is preferably 0.01-10 mm. Therefore, the quality of the titanium-based coating can be optimized while the cost is effectively controlled, the uniformity of the coating is ensured, and the performance of the metal electrode plate of the titanium-based coated fuel cell is optimized.
The thickness of the pretreated titanium alloy polar plate substrate is 0.001 mm-0.1 mm thinner than that of the titanium alloy polar plate substrate. In this way, the titanium-based coated fuel cell metal plate performance can be optimized.
The pretreatment is realized by the following method: and (3) placing the titanium alloy polar plate substrate on a polishing disc for polishing (in the embodiment of the application, the polishing conditions are 3000-5000 r/min for 5-10 min), so as to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In a preferred embodiment, in step S02,
the heating rate is preferably 10 to 50 ℃/min.
The flow rate of the oxygen gas is preferably 10sccm to 100sccm.
In a preferred embodiment, in step S03,
the carbon source gas is preferably CH 4 、C 2 H 2 CO or C 2 H 4 And (3) waiting for gas. The carbon source gas can be CVD (Chemical Vapor Deposition ) or PVD (Physical Vapor Deposition, physical vapor deposition)Product) is deposited, CVD is preferred in the examples of the present application.
The flow rate of the carbon source gas is preferably 10sccm to 100sccm.
The heating rate is preferably 10 to 50 ℃/min.
In step S03, a reduction reaction is performed by covering the surface with the titanium oxide transition layer and the carbon source gas, so that the carbon element is deposited on the surface of the substrate.
In a preferred embodiment, in step S04,
the rare gas is preferably argon.
The flow rate of the rare gas is 50sccm to 200sccm. Thus, a layer of compact titanium carbide can be prepared on the surface of the titanium alloy matrix, thereby achieving the effects of enhancing the conductivity, corrosion resistance and mechanical property of the metal polar plate of the fuel cell and meeting the high-performance and long-time use requirements of the metal polar plate of the fuel cell.
The catalyst is preferably metallic chromium; the specific amount of catalyst used is dependent on the area of the plate, preferably 0.02g/cm 2 ~0.08g/cm 2
The heating rate is preferably 10 to 50 ℃/min. Thus, a layer of compact titanium carbide can be prepared on the surface of the titanium alloy matrix, and the compact uniformity of the titanium carbide is ensured.
In step S04, the mechanism for generating the titanium-based coating of the titanium-based coated fuel cell metal plate is:
TiO 2 +3C→TiC+2CO。
on the other hand, the embodiment of the application also provides the titanium-based coating fuel cell metal polar plate obtained by the preparation method.
According to the method, a layer of compact titanium carbide is prepared on the surface of the titanium alloy substrate, so that the effects of enhancing the conductivity, corrosion resistance and mechanical property of the metal electrode plate of the fuel cell are achieved, the high-performance and long-time use requirements of the metal electrode plate of the fuel cell are met, and the problems that the existing metal electrode plate is easy to corrode in a proton exchange membrane fuel cell environment, metal ions capable of poisoning a catalyst are released after the metal electrode plate corrodes, or a compact oxide film capable of increasing interface contact resistance is formed, the output power and the service life of the fuel cell are greatly influenced and the like can be solved. The preparation method disclosed by the invention is simple, is more environment-friendly, has lower production cost and higher production efficiency, and is easy for batch or large-scale production.
In the embodiment of the application, the prepared titanium-based coated fuel cell metal polar plate has the tensile strength of 550-720 Mpa, the compressive strength of 430-640 Mpa, the resistivity of 0.22-0.30 microohm-m at normal temperature, and the corrosion rate of the polar plate per hundred hours measured by adopting a weight increasing method is 0.15mg/cm 2 ~0.24mg/cm 2
Example 1
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 500 ℃, and then introducing oxygen to react for 1.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800 ℃, and then carrying out carbon deposition reaction for 10min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200 ℃ and reacting for 30min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is preferably 0.1mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 20 ℃/min.
The flow rate of the oxygen gas was 30sccm.
In the step S03 of the process,
the carbon source gas is CH 4
The flow rate of the carbon source gas was 40sccm.
The heating speed is 20 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas is 200sccm.
The heating speed is 15 ℃/min.
The prepared titanium-based coated fuel cell metal polar plate has the tensile strength of 550Mpa, the compressive strength of 430Mpa, the resistivity of 0.3 micro ohm-meter at normal temperature, and the corrosion rate of the polar plate per hundred hours measured by adopting a weight increasing method is 0.15mg/cm 2
Example 2
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 450 ℃, and then introducing oxygen to react for 1.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 900 ℃, and then carrying out carbon deposition reaction for 15min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1300 ℃ and reacting for 50min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is 0.2mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 15 ℃/min.
The flow rate of the oxygen gas was 30sccm.
In the step S03 of the process,
the carbon source gas is C 2 H 2
The flow rate of the carbon source gas was 40sccm.
The heating speed is 15 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is preferably argon.
The flow rate of the rare gas was 150sccm.
The heating speed is 25 ℃/min.
The prepared titanium-based coated fuel cell metal polar plate has the tensile strength of 720Mpa, the compressive strength of 640Mpa, the resistivity of 0.28 micro ohm-meter at normal temperature, and the corrosion rate of the polar plate per hundred hours measured by adopting a weight increasing method is 0.18mg/cm 2
Example 3
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 600 ℃, and then introducing oxygen to react for 1.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 1000 ℃, and then carrying out carbon deposition reaction for 15min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer with carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1500 ℃ and reacting for 60min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is 0.15mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 25 ℃/min.
The flow rate of the oxygen gas was 35sccm.
In the step S03 of the process,
the carbon source gasThe body is CH 4
The flow rate of the carbon source gas was 60sccm.
The heating speed is 25 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas is 100sccm.
The heating speed is 25 ℃/min.
The prepared titanium-based coated fuel cell metal polar plate has tensile strength of 600Mpa, compressive strength of 500Mpa, resistivity of 0.22 microohm-meter at normal temperature, and corrosion rate of 0.24mg/cm per hundred hours measured by adopting a weight increasing method 2
Example 4
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 300 ℃, and then introducing oxygen to react for 2.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800 ℃, and then carrying out carbon deposition reaction for 100min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200 ℃ and reacting for 100min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is 10mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 50 ℃/min.
The flow rate of the oxygen gas is 100sccm.
In the step S03 of the process,
the carbon source gas is CO.
The flow rate of the carbon source gas is 100sccm.
The heating speed is 50 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas is 200sccm.
The heating speed is 50 ℃/min.
The prepared titanium-based coated fuel cell metal polar plate has the tensile strength of 720Mpa, the compressive strength of 640Mpa, the resistivity of 0.30 microohm-meter at normal temperature, and the corrosion rate of the polar plate per hundred hours measured by adopting a weight increasing method is 0.24mg/cm 2
Example 5
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 600 ℃, and then introducing oxygen to react for 0.1h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800 ℃, and then carrying out carbon deposition reaction for 1min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer with carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1500 ℃ and reacting for 1min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is 0.05mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.001 mm-0.01 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 10 ℃/min.
The flow rate of the oxygen gas was 10sccm.
In the step S03 of the process,
the carbon source gas is C 2 H 4
The flow rate of the carbon source gas was 10sccm.
The heating speed is 10 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas was 50sccm.
The heating speed is 10 ℃/min.
The prepared titanium-based coating fuel cell metal polar plate has tensile strength of 580Mpa, compressive strength of 470Mpa, resistivity of 0.23 microohm-meter at normal temperature, and adopts the increaseThe corrosion rate of the polar plate measured by a gravimetric method is 0.18mg/cm per hundred hours 2
Comparative example 1
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 500 ℃, and then introducing oxygen to react for 1.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800 ℃, and then carrying out carbon deposition reaction for 10min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200 ℃ and reacting for 30min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is preferably 0.1mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 20 ℃/min.
The flow rate of the oxygen gas was 30sccm.
In the step S03 of the process,
the carbon source gas is CH 4
The flow rate of the carbon source gas was 40sccm.
The heating speed is 20 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas was 40sccm.
The heating speed is 15 ℃/min.
The prepared titanium-based coated fuel cell metal polar plate has the tensile strength of 550Mpa, the compressive strength of 430Mpa, the resistivity of 0.28 microohm-meter at normal temperature, and the corrosion rate of the polar plate per hundred hours measured by adopting a weight increasing method is 0.13mg/cm 2
Comparative example 2
A preparation method of a titanium-based coated fuel cell metal polar plate comprises the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 500 ℃, and then introducing oxygen to react for 1.0h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800 ℃, and then carrying out carbon deposition reaction for 10min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer and carbon deposited on the surface;
and S04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1000 ℃ and reacting for 110min to obtain the titanium-based coated fuel cell metal polar plate.
In the step S01 of the process,
the thickness of the titanium alloy polar plate substrate is preferably 0.1mm.
The thickness of the pretreated titanium alloy polar plate substrate is 0.01-0.02 mm thinner than that of the titanium alloy polar plate substrate.
The pretreatment is realized by the following method: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
In the embodiment of the application, the polishing disc is a polishing disc attached with sand paper, and the surface of the titanium alloy polar plate substrate is polished and ground through high-speed rotation of the polishing disc so as to remove a mechanical damage layer and a stress layer on the surface of the titanium alloy polar plate substrate, and a clean titanium alloy polar plate substrate (namely, a pretreated titanium alloy polar plate substrate) is obtained.
In step S02 of the process,
the heating speed is 20 ℃/min.
The flow rate of the oxygen gas was 30sccm.
In the step S03 of the process,
the carbon source gas is CH 4
The flow rate of the carbon source gas was 40sccm.
The heating speed is 20 ℃/min.
In step S04 the process proceeds to the step of,
the rare gas is argon.
The flow rate of the rare gas is 200sccm.
The heating speed is 15 ℃/min.
The prepared titanium-based coating fuel cell metal polar plate has tensile strength of 450Mpa, compressive strength of 330Mpa, resistivity of 0.18 microohm-meter at normal temperature, and corrosion rate of 0.25mg/cm per hundred hours measured by adopting a weight increasing method 2
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.

Claims (10)

1. The preparation method of the titanium-based coated fuel cell metal polar plate is characterized by comprising the following steps:
s01, preprocessing a titanium alloy polar plate matrix to obtain a preprocessed titanium alloy polar plate matrix;
s02, heating the pretreated titanium alloy polar plate substrate in the step S01 to 300-600 ℃, and then introducing oxygen to react for 0.1-2.0 h to obtain the titanium alloy polar plate substrate with the surface covered with the titanium oxide transition layer;
s03, introducing carbon source gas into the titanium alloy polar plate substrate with the titanium oxide transition layer covered on the surface in the step S02, heating to 800-1000 ℃, and then carrying out carbon deposition reaction for 1-100 min to obtain the titanium alloy polar plate substrate with the titanium oxide transition layer with carbon deposited on the surface;
s04, introducing rare gas into the titanium alloy polar plate substrate of the titanium oxide transition layer with carbon deposited on the surface in the step S03, then adding a catalyst, heating to 1200-1500 ℃ and reacting for 1-100 min to obtain a titanium-based coating fuel cell metal polar plate;
the flow rate of the carbon source gas is 10 sccm-100 sccm;
the flow rate of the rare gas is 50 sccm-200 sccm;
the catalyst is metallic chromium; the specific dosage of the catalyst is 0.02g/cm 2 ~0.08g/cm 2
2. The method for preparing a metal electrode plate of a titanium-based coated fuel cell according to claim 1, wherein in the step S01, the thickness of the titanium alloy electrode plate substrate is 0.01mm to 10mm.
3. The method for preparing a titanium-based coated fuel cell metal plate according to claim 2, wherein the thickness of the pretreated titanium alloy plate substrate is 0.001mm to 0.1mm thinner than the thickness of the titanium alloy plate substrate.
4. The method for preparing a metal plate of a titanium-based coated fuel cell according to claim 1, wherein in step S01, the pretreatment is performed by: and placing the titanium alloy polar plate substrate on a polishing disc for polishing to obtain the pretreated titanium alloy polar plate substrate.
5. The method for producing a metal electrode plate for a titanium-based coated fuel cell according to claim 1, wherein in step S02, the heating rate is 10 ℃/min to 50 ℃/min.
6. The method for producing a metal electrode plate for a titanium-based coated fuel cell according to claim 1, wherein in step S02, the flow rate of oxygen gas is 10sccm to 100sccm.
7. The method for producing a metal electrode plate of a titanium-based coated fuel cell according to claim 1, wherein in step S03, the carbon source gas is CH 4 、C 2 H 2 CO or C 2 H 4
8. The method of producing a titanium-based coated fuel cell metal plate according to claim 7, wherein the heating rate is 10 ℃/min to 50 ℃/min.
9. The method for producing a titanium-based coated fuel cell metal plate according to claim 1, wherein, in step S04,
the rare gas is argon;
the heating speed is 10-50 ℃/min.
10. A titanium-based coated fuel cell metal plate prepared by the method of any one of claims 1 to 9.
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JP2014022250A (en) * 2012-07-20 2014-02-03 Kobe Steel Ltd Fuel cell separator
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