CN111933965A - High-temperature fuel cell bipolar plate oxidation-resistant coating - Google Patents
High-temperature fuel cell bipolar plate oxidation-resistant coating Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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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
- C23C14/0021—Reactive sputtering or evaporation
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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
- C23C14/0641—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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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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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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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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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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract
The invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell, and relates to the technical field of fuel cells. The high-temperature fuel cell bipolar plate oxidation resistant coating comprises a composite coating, wherein the composite coating consists of a CrN film layer, a silver coating and a gold coating; the preparation method of the oxidation-resistant plating layer comprises the following steps: 1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate; 2) depositing the generated film on the surface of a stainless steel plate to obtain a CrN film layer; 3) plating a silver plating layer on the CrN film layer; 4) and plating a gold plating layer on the silver plating layer. The invention can reduce the contact resistance of the bipolar plate, and because the silver has good conductivity, the contact resistance of the stainless steel plate after being plated with silver can be further reduced, and the binding force of the plating layer is good; electroplating or sputtering a small amount of thin gold on the silver layer can well solve the problem of weak bonding of the gold plating layer, and obtain good conductivity and smaller contact resistance.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell.
Background
The principle of the fuel cell is an electrochemical device, and the composition of the fuel cell is the same as that of a general battery. The single cell is composed of a positive electrode and a negative electrode (a negative electrode, namely a fuel electrode, and a positive electrode, namely an oxidant electrode) and an electrolyte. Except that the active material of a general battery is stored inside the battery, and thus, the battery capacity is limited. The positive and negative electrodes of the fuel cell do not contain active materials themselves, but are catalytic conversion elements. Fuel cells are thus well-known energy conversion machines that convert chemical energy into electrical energy. When the cell is operated, the fuel and the oxidant are supplied from the outside to react. In principle, the fuel cell can generate electricity continuously as long as reactants are continuously fed and reaction products are continuously discharged.
The bipolar plate is one of the key components of the fuel cell, the bipolar plate plays roles of providing a gas reaction site, collecting current, supporting a membrane electrode, managing water and the like, the bipolar plate material has good electrical conductivity, stronger corrosion resistance, higher mechanical strength and low cost, the graphite and graphite-based composite material has lower contact resistance and stronger corrosion resistance and is applied to the fuel cell plate, however, the graphite material has poor mechanical strength, is difficult to process in large batch, limits the wide application, has good electrical conductivity and strong vibration resistance, is suitable for stamping and forming mass production, and is the main development direction of the metal polar plate of the fuel cell, however, the metal polar plate is corroded in the working environment of the fuel cell with strong acid, high temperature and high humidity, the metal ion pollutes the catalyst, the conductivity of the proton exchange membrane is reduced, and the service life of the fuel cell is seriously influenced; meanwhile, the metal polar plate is easy to form a protective passive film in an acid environment, so that the contact resistance between the polar plate and the gas diffusion layer is increased, and the output performance of the fuel cell is reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell, which solves the defects and shortcomings in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the anti-oxidation coating of the bipolar plate of the high-temperature fuel cell comprises a composite coating, wherein the composite coating consists of a CrN film layer, a silver coating and a gold coating;
the preparation method of the oxidation-resistant plating layer comprises the following steps:
1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate;
2) firstly, ionizing a target material to be plated by utilizing a vacuum arc, introducing reaction gas to form vacuum plasma, reacting the vacuum plasma in a space of a deposition chamber, generating a thin film and depositing the thin film on the surface of a stainless steel plate to obtain a CrN film layer;
3) plating a silver plating layer on the CrN film layer;
4) plating a gold plating layer on the silver plating layer;
5) and (5) detecting the oxidation resistant plating layer of the bipolar plate.
Preferably, the stainless steel plate is pretreated in the step 1, specifically as follows:
i) firstly, adding water into a detergent, uniformly stirring, then putting the mixture into a stainless steel plate, soaking for 30-60min, then scrubbing for 2-3 times by using a sponge ball, and then washing the sponge ball clean by using deionized water; then, placing the stainless steel plate into 20-30% hydrochloric acid solution to be soaked for 30-40min, then scrubbing for 2-3 times by using a steel wire ball, and then washing by using deionized water;
ii) grinding and polishing the treated stainless steel plate, then cleaning the stainless steel plate for 2-3 times by using alcohol, finally removing the alcohol on the surface of the stainless steel plate by using deionized water, and drying the cleaned stainless steel plate in a vacuum environment at the drying temperature of 40-50 ℃.
Preferably, the CrN film layer obtained in step 2 is specifically as follows: the metal Cr is arranged on a target position of the deposition chamber, and the deposition chamber is vacuumized to 7-8x10-3And Pa, then beginning to introduce argon, applying a bias voltage of-500V in a pulse mode, controlling the frequency to be 15-20KHz, adjusting the partial pressure of the argon to be 0.4-0.6Pa, igniting two Cr arcs, beginning to perform deposition treatment, introducing nitrogen into the deposition chamber to begin to deposit a CrN film layer, controlling the flow of the nitrogen to be 80-120sccm, stopping introducing the nitrogen after 15-25min of deposition, beginning to deposit a Cr film layer, and depositing for 2-4 min.
Preferably, in the step 3, a silver plating layer is plated on the CrN film layer, specifically as follows: firstly, preparing silver plating solution, and carrying out silver plating treatment on the stainless steel plate deposited with the CrN film layer, wherein the silver plating temperature is room temperature, and the current density is 0.7-1.2A/dm2The anode material is porous carbon paper in the silver plating process, and the electroplating time is 50-70 min.
Preferably, the silver plating solution adopted in the silver plating process comprises 60-80mL/L of ammonia water, 20-30g/L of silver nitrate, 5-10g/L of silver ion complexing agent, 20-30g/L of sodium pyrophosphate, 40-60g/L of ammonium sulfate, 40-60g/L of sodium nitrate and 1-2g/L of surfactant.
Preferably, in the step 4, a gold plating layer is plated on the silver plating layer, specifically as follows: firstly, preparing gold plating solution, and carrying out gold plating treatment on the stainless steel plate plated with the silver layer, wherein the gold plating temperature is 50-60 ℃, and the cathode current density is 0.2-0.6A/dm2Controlling the pH value of the gold plating solution to be 8.5-9.5, wherein the anode material is porous carbon paper, and the gold plating treatment time is 10-20 min.
Preferably, the gold plating solution used in the gold plating process comprises 0.4-0.6g/L of gold potassium cyanide, 240g/L of ammonium sulfite, 80-100g/L of potassium citrate and 20-40g/L of potassium carbonate.
(III) advantageous effects
The invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell. The method has the following beneficial effects:
1. the invention can reduce the contact resistance of the bipolar plate, and because the silver has good conductivity, the contact resistance of the stainless steel plate after being plated with silver can be further reduced, and the binding force of the plating layer is good; electroplating or sputtering a small amount of thin gold on the silver layer can well solve the problem of weak bonding of the gold plating layer, and obtain good conductivity and smaller contact resistance.
2. Compared with the traditional graphite and graphite-based composite material, the bipolar plate can be produced in batch, has good electrical conductivity and strong anti-vibration capability, is suitable for stamping and forming mass production, is not easy to corrode in the strong acid, high temperature and high humidity fuel cell working environment, and prolongs the service life.
3. According to the invention, the impact resistance of the bipolar plate can be increased through the CrN film layer, so that the service life of the fuel cell is prolonged, the hardness of the CrN film layer is increased to improve the performance of the fuel cell, and meanwhile, the attached Cr film layer can also be in full contact with the diffusion layer.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the embodiment of the invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell, which comprises a composite coating, wherein the composite coating consists of a CrN film layer, a silver coating and a gold coating;
the preparation method of the anti-oxidation coating comprises the following steps:
1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate, wherein the pretreatment comprises the following steps:
i) firstly, adding water into a detergent, uniformly stirring, then putting the mixture into a stainless steel plate, soaking for 30-60min, then scrubbing for 2-3 times by using a sponge ball, and then washing the sponge ball clean by using deionized water; then, placing the stainless steel plate into 20-30% hydrochloric acid solution to be soaked for 30-40min, then scrubbing for 2-3 times by using a steel wire ball, and then washing by using deionized water;
ii) grinding and polishing the treated stainless steel plate, then cleaning the stainless steel plate for 2-3 times by using alcohol, finally removing the alcohol on the surface of the stainless steel plate by using deionized water, and drying the cleaned stainless steel plate in a vacuum environment at the drying temperature of 40-50 ℃;
2) firstly, a target material to be plated is ionized by a vacuum arc, then reaction gas is introduced to form vacuum plasma, the vacuum plasma reacts in a space of a deposition chamber, and a thin film is generated and deposited on the surface of a stainless steel plateObtaining a CrN film layer as follows: the metal Cr is arranged on a target position of the deposition chamber, and the deposition chamber is vacuumized to 7-8x10-3Pa, then beginning to introduce argon, applying-500V bias voltage as a pulse mode, controlling the frequency to be 15-20KHz, adjusting the argon partial pressure to be 0.4-0.6Pa, igniting two Cr arcs, beginning to perform deposition treatment, introducing nitrogen into the deposition chamber to begin to deposit a CrN film layer, controlling the nitrogen flow to be 80-120sccm, stopping introducing nitrogen after depositing for 15-25min, beginning to deposit a Cr film layer, and depositing for 2-4 min;
3) plating a silver plating layer on the CrN film layer, which comprises the following steps: firstly, preparing silver plating solution, and carrying out silver plating treatment on the stainless steel plate deposited with the CrN film layer, wherein the silver plating temperature is room temperature, and the current density is 0.7-1.2A/dm2In the silver plating process, the anode material is porous carbon paper, the electroplating time is 50-70min, and the silver plating solution comprises 60mL/L of ammonia water, 20g/L of silver nitrate, 5g/L of silver ion complexing agent, 20g/L of sodium pyrophosphate, 40g/L of ammonium sulfate, 40g/L of sodium nitrate and 1g/L of surfactant;
4) plating a gold plating layer on the silver plating layer, which comprises the following steps: firstly, preparing gold plating solution, and carrying out gold plating treatment on the stainless steel plate plated with the silver layer, wherein the gold plating temperature is 50-60 ℃, and the cathode current density is 0.2-0.6A/dm2Controlling the pH value of the gold plating solution to be between 8.5 and 9.5, wherein the anode material is porous carbon paper, the gold plating treatment time is 10 to 20min, and the gold plating solution comprises 0.4g/L of gold potassium cyanide, 120g/L of ammonium sulfite, 80g/L of potassium citrate and 20g/L of potassium carbonate;
5) and (5) detecting the oxidation resistant plating layer of the bipolar plate.
Compared with the traditional graphite and graphite-based composite material, the bipolar plate can be produced in batch, has good electrical conductivity and strong anti-vibration capability, is suitable for stamping and forming mass production, is not easy to corrode in the strong acid, high temperature and high humidity fuel cell working environment, and prolongs the service life.
Example two:
the embodiment of the invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell, which comprises a composite coating, wherein the composite coating consists of a CrN film layer, a silver coating and a gold coating;
the preparation method of the anti-oxidation coating comprises the following steps:
1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate, wherein the pretreatment comprises the following steps:
i) firstly, adding water into a detergent, uniformly stirring, then putting the mixture into a stainless steel plate, soaking for 30-60min, then scrubbing for 2-3 times by using a sponge ball, and then washing the sponge ball clean by using deionized water; then, placing the stainless steel plate into 20-30% hydrochloric acid solution to be soaked for 30-40min, then scrubbing for 2-3 times by using a steel wire ball, and then washing by using deionized water;
ii) grinding and polishing the treated stainless steel plate, then cleaning the stainless steel plate for 2-3 times by using alcohol, finally removing the alcohol on the surface of the stainless steel plate by using deionized water, and drying the cleaned stainless steel plate in a vacuum environment at the drying temperature of 40-50 ℃;
2) firstly, ionizing a target material to be plated by utilizing a vacuum arc, introducing reaction gas to form vacuum plasma, reacting the vacuum plasma in a space of a deposition chamber, generating a thin film and depositing the thin film on the surface of a stainless steel plate to obtain a CrN film layer, wherein the method comprises the following steps: the metal Cr is arranged on a target position of the deposition chamber, and the deposition chamber is vacuumized to 7-8x10-3Pa, then beginning to introduce argon, applying-500V bias voltage as a pulse mode, controlling the frequency to be 15-20KHz, adjusting the argon partial pressure to be 0.4-0.6Pa, igniting two Cr arcs, beginning to perform deposition treatment, introducing nitrogen into the deposition chamber to begin to deposit a CrN film layer, controlling the nitrogen flow to be 80-120sccm, stopping introducing nitrogen after depositing for 15-25min, beginning to deposit a Cr film layer, and depositing for 2-4 min;
3) plating a silver plating layer on the CrN film layer, which comprises the following steps: firstly, preparing silver plating solution, and carrying out silver plating treatment on the stainless steel plate deposited with the CrN film layer, wherein the silver plating temperature is room temperature, and the current density is 0.7-1.2A/dm2In the silver plating process, the anode material is porous carbon paper, the electroplating time is 50-70min, and the silver plating solution comprises 70mL/L of ammonia water, 25g/L of silver nitrate, 7.5g/L of silver ion complexing agent, 25g/L of sodium pyrophosphate, 50g/L of ammonium sulfate, 50g/L of sodium nitrate and 1.5g/L of surfactant;
4) plating a gold layer on the silver layer, such asThe following: firstly, preparing gold plating solution, and carrying out gold plating treatment on the stainless steel plate plated with the silver layer, wherein the gold plating temperature is 50-60 ℃, and the cathode current density is 0.2-0.6A/dm2Controlling the pH value of the gold plating solution to be between 8.5 and 9.5, wherein the anode material is porous carbon paper, the gold plating treatment time is 10 to 20min, and the gold plating solution comprises 0.5g/L of gold potassium cyanide, 180g/L of ammonium sulfite, 90g/L of potassium citrate and 30g/L of potassium carbonate;
5) and (5) detecting the oxidation resistant plating layer of the bipolar plate.
Example three:
the embodiment of the invention provides an anti-oxidation coating of a bipolar plate of a high-temperature fuel cell, which comprises a composite coating, wherein the composite coating consists of a CrN film layer, a silver coating and a gold coating;
the preparation method of the anti-oxidation coating comprises the following steps:
1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate, wherein the pretreatment comprises the following steps:
i) firstly, adding water into a detergent, uniformly stirring, then putting the mixture into a stainless steel plate, soaking for 30-60min, then scrubbing for 2-3 times by using a sponge ball, and then washing the sponge ball clean by using deionized water; then, placing the stainless steel plate into 20-30% hydrochloric acid solution to be soaked for 30-40min, then scrubbing for 2-3 times by using a steel wire ball, and then washing by using deionized water;
ii) grinding and polishing the treated stainless steel plate, then cleaning the stainless steel plate for 2-3 times by using alcohol, finally removing the alcohol on the surface of the stainless steel plate by using deionized water, and drying the cleaned stainless steel plate in a vacuum environment at the drying temperature of 40-50 ℃;
2) firstly, ionizing a target material to be plated by utilizing a vacuum arc, introducing reaction gas to form vacuum plasma, reacting the vacuum plasma in a space of a deposition chamber, generating a thin film and depositing the thin film on the surface of a stainless steel plate to obtain a CrN film layer, wherein the method comprises the following steps: the metal Cr is arranged on a target position of the deposition chamber, and the deposition chamber is vacuumized to 7-8x10-3Pa, introducing argon, applying-500V bias voltage as pulse mode, adjusting argon partial pressure to 0.4-0.6Pa, igniting two Cr arcs, starting deposition, introducing nitrogen into the deposition chamber, and openingDepositing a CrN film layer at the flow rate of 80-120sccm, stopping introducing nitrogen after depositing for 15-25min, and depositing a Cr film layer for 2-4 min;
3) plating a silver plating layer on the CrN film layer, which comprises the following steps: firstly, preparing silver plating solution, and carrying out silver plating treatment on the stainless steel plate deposited with the CrN film layer, wherein the silver plating temperature is room temperature, and the current density is 0.7-1.2A/dm2In the silver plating process, the anode material is porous carbon paper, the electroplating time is 50-70min, and the silver plating solution comprises 80mL/L of ammonia water, 30g/L of silver nitrate, 10g/L of silver ion complexing agent, 30g/L of sodium pyrophosphate, 60g/L of ammonium sulfate, 60g/L of sodium nitrate and 2g/L of surfactant;
4) plating a gold plating layer on the silver plating layer, which comprises the following steps: firstly, preparing gold plating solution, and carrying out gold plating treatment on the stainless steel plate plated with the silver layer, wherein the gold plating temperature is 50-60 ℃, and the cathode current density is 0.2-0.6A/dm2Controlling the pH value of the gold plating solution to be between 8.5 and 9.5, wherein the anode material is porous carbon paper, the gold plating treatment time is 10 to 20min, and the gold plating solution comprises 0.6g/L of gold potassium cyanide, 240g/L of ammonium sulfite, 100g/L of potassium citrate and 40g/L of potassium carbonate;
5) and (5) detecting the oxidation resistant plating layer of the bipolar plate.
The invention can reduce the contact resistance of the bipolar plate, and because the silver has good conductivity, the contact resistance of the stainless steel plate after being plated with silver can be further reduced, and the binding force of the plating layer is good; electroplating or sputtering a small amount of thin gold on the silver layer can well solve the problem of weak bonding of the gold plating layer, and obtain good conductivity and smaller contact resistance.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The utility model provides a high temperature fuel cell bipolar plate oxidation resistant coating which characterized in that: the bipolar plate antioxidant coating comprises a composite coating, and the composite coating consists of a CrN film layer, a silver coating and a gold coating;
the preparation method of the oxidation-resistant plating layer comprises the following steps:
1) selecting a stainless steel plate as a bipolar plate material, and pretreating the stainless steel plate;
2) firstly, ionizing a target material to be plated by utilizing a vacuum arc, introducing reaction gas to form vacuum plasma, reacting the vacuum plasma in a space of a deposition chamber, generating a thin film and depositing the thin film on the surface of a stainless steel plate to obtain a CrN film layer;
3) plating a silver plating layer on the CrN film layer;
4) plating a gold plating layer on the silver plating layer;
5) and (5) detecting the oxidation resistant plating layer of the bipolar plate.
2. The oxidation-resistant coating for the bipolar plate of the high-temperature fuel cell as claimed in claim 1, wherein: in the step 1, the stainless steel plate is pretreated, specifically as follows:
i) firstly, adding water into a detergent, uniformly stirring, then putting the mixture into a stainless steel plate, soaking for 30-60min, then scrubbing for 2-3 times by using a sponge ball, and then washing the sponge ball clean by using deionized water; then, placing the stainless steel plate into 20-30% hydrochloric acid solution to be soaked for 30-40min, then scrubbing for 2-3 times by using a steel wire ball, and then washing by using deionized water;
ii) grinding and polishing the treated stainless steel plate, then cleaning the stainless steel plate for 2-3 times by using alcohol, finally removing the alcohol on the surface of the stainless steel plate by using deionized water, and drying the cleaned stainless steel plate in a vacuum environment at the drying temperature of 40-50 ℃.
3. The oxidation-resistant coating for the bipolar plate of the high-temperature fuel cell as claimed in claim 1, wherein: the CrN film layer obtained in the step 2 is specifically as follows: the metal Cr is arranged on a target position of the deposition chamber, and the deposition chamber is vacuumized to 7-8x10- 3And Pa, then beginning to introduce argon, applying a bias voltage of-500V in a pulse mode, controlling the frequency to be 15-20KHz, adjusting the partial pressure of the argon to be 0.4-0.6Pa, igniting two Cr arcs, beginning to perform deposition treatment, introducing nitrogen into the deposition chamber to begin to deposit a CrN film layer, controlling the flow of the nitrogen to be 80-120sccm, stopping introducing the nitrogen after 15-25min of deposition, beginning to deposit a Cr film layer, and depositing for 2-4 min.
4. The oxidation-resistant coating for the bipolar plate of the high-temperature fuel cell as claimed in claim 1, wherein: in the step 3, a silver plating layer is plated on the CrN film layer, which comprises the following specific steps: firstly, preparing silver plating solution, and carrying out silver plating treatment on the stainless steel plate deposited with the CrN film layer, wherein the silver plating temperature is room temperature, and the current density is 0.7-1.2A/dm2The anode material is porous carbon paper in the silver plating process, and the electroplating time is 50-70 min.
5. The oxidation-resistant coating for the bipolar plate of the high-temperature fuel cell as claimed in claim 4, wherein: the silver plating solution adopted in the silver plating process comprises 60-80mL/L of ammonia water, 20-30g/L of silver nitrate, 5-10g/L of silver ion complexing agent, 20-30g/L of sodium pyrophosphate, 40-60g/L of ammonium sulfate, 40-60g/L of sodium nitrate and 1-2g/L of surfactant.
6. The high-temperature fuel cell bipolar plate oxidation resistant coating according to claim 1,the method is characterized in that: in the step 4, a gold plating layer is plated on the silver plating layer, which comprises the following specific steps: firstly, preparing gold plating solution, and carrying out gold plating treatment on the stainless steel plate plated with the silver layer, wherein the gold plating temperature is 50-60 ℃, and the cathode current density is 0.2-0.6A/dm2Controlling the pH value of the gold plating solution to be 8.5-9.5, wherein the anode material is porous carbon paper, and the gold plating treatment time is 10-20 min.
7. The oxidation-resistant coating for the bipolar plate of the high-temperature fuel cell as claimed in claim 6, wherein: the gold plating solution adopted in the gold plating process comprises 0.4-0.6g/L of gold potassium cyanide, 240g/L of ammonium sulfite, 80-100g/L of potassium citrate and 20-40g/L of potassium carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593264A (en) * | 2020-11-17 | 2021-04-02 | 东风汽车集团有限公司 | Method for repairing surface coating of metal bipolar plate |
| CN112820890A (en) * | 2020-12-25 | 2021-05-18 | 格力电器（武汉）有限公司 | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276916A (en) * | 2008-05-15 | 2008-10-01 | 大连交通大学 | Preparation technique for anti-corrosion fuel cell stainless dual-polar plate |
| CN101667647A (en) * | 2009-08-17 | 2010-03-10 | 新源动力股份有限公司 | Bipolar plate for proton exchange membrane fuel cell |
| CN102629690A (en) * | 2012-04-20 | 2012-08-08 | 大连交通大学 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
| CN102936740A (en) * | 2012-11-19 | 2013-02-20 | 成都泛华航空仪表电器有限公司 | Gold-silver-rhodium multilayer composite plating process |
| KR20140094736A (en) * | 2013-01-22 | 2014-07-31 | (주)제이 앤 엘 테크 | Method for manufacturing corrosion resistant and conductive nano carbon coating and fuel cell bipolar plate thereby |
| CN105895927A (en) * | 2015-02-12 | 2016-08-24 | 福特全球技术公司 | Corrosion Resistant Metal Bipolar Plate for a PEMFC Including a Radical Scavenger |
| CN107406961A (en) * | 2015-03-20 | 2017-11-28 | 艾普伦 | The manufacture method of metal tape or thin slice, bipolar plates and correlation with chromium nitride coating |
| KR20180071495A (en) * | 2016-12-20 | 2018-06-28 | 삼보모터스주식회사 | Separator for fuel cell |
| CN109301259A (en) * | 2018-09-30 | 2019-02-01 | 重庆大学 | A kind of dual polar plates of proton exchange membrane fuel cell and preparation method thereof |
| CN111218656A (en) * | 2019-11-25 | 2020-06-02 | 江苏氢电新能源有限公司 | High-corrosion-resistance high-conductivity fuel cell metal bipolar plate protective film and preparation method thereof |
-
2020
- 2020-07-24 CN CN202010723351.0A patent/CN111933965A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101276916A (en) * | 2008-05-15 | 2008-10-01 | 大连交通大学 | Preparation technique for anti-corrosion fuel cell stainless dual-polar plate |
| CN101667647A (en) * | 2009-08-17 | 2010-03-10 | 新源动力股份有限公司 | Bipolar plate for proton exchange membrane fuel cell |
| CN102629690A (en) * | 2012-04-20 | 2012-08-08 | 大连交通大学 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
| CN102936740A (en) * | 2012-11-19 | 2013-02-20 | 成都泛华航空仪表电器有限公司 | Gold-silver-rhodium multilayer composite plating process |
| KR20140094736A (en) * | 2013-01-22 | 2014-07-31 | (주)제이 앤 엘 테크 | Method for manufacturing corrosion resistant and conductive nano carbon coating and fuel cell bipolar plate thereby |
| CN105895927A (en) * | 2015-02-12 | 2016-08-24 | 福特全球技术公司 | Corrosion Resistant Metal Bipolar Plate for a PEMFC Including a Radical Scavenger |
| CN107406961A (en) * | 2015-03-20 | 2017-11-28 | 艾普伦 | The manufacture method of metal tape or thin slice, bipolar plates and correlation with chromium nitride coating |
| KR20180071495A (en) * | 2016-12-20 | 2018-06-28 | 삼보모터스주식회사 | Separator for fuel cell |
| CN109301259A (en) * | 2018-09-30 | 2019-02-01 | 重庆大学 | A kind of dual polar plates of proton exchange membrane fuel cell and preparation method thereof |
| CN111218656A (en) * | 2019-11-25 | 2020-06-02 | 江苏氢电新能源有限公司 | High-corrosion-resistance high-conductivity fuel cell metal bipolar plate protective film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 中国科学技术信息研究所 钢铁研究总院 中国工程院 编著: "《汉语科技词系统（有色金属卷）》", 30 April 2017 * |
| 文雯: "不锈钢双极板表面纳米Cr及CrN涂层的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593264A (en) * | 2020-11-17 | 2021-04-02 | 东风汽车集团有限公司 | Method for repairing surface coating of metal bipolar plate |
| CN112593264B (en) * | 2020-11-17 | 2022-03-01 | 东风汽车集团有限公司 | Method for repairing surface coating of metal bipolar plate |
| CN112820890A (en) * | 2020-12-25 | 2021-05-18 | 格力电器（武汉）有限公司 | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate |
| CN112820890B (en) * | 2020-12-25 | 2022-09-16 | 格力电器（武汉）有限公司 | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate |
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