CN114875464B - Preparation method of anode bipolar plate of PEM (PEM) electrolytic tank - Google Patents
Preparation method of anode bipolar plate of PEM (PEM) electrolytic tank Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 238000005520 cutting process Methods 0.000 claims abstract description 14
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- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 238000005238 degreasing Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 229910018487 Ni—Cr Inorganic materials 0.000 claims abstract description 8
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 4
- 238000005275 alloying Methods 0.000 claims abstract description 3
- 238000005554 pickling Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
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- 238000007254 oxidation reaction Methods 0.000 abstract description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910003298 Ni-Ni Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/036—Bipolar electrodes
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
- C25D5/48—After-treatment of electroplated surfaces
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a preparation method of an anode bipolar plate of a PEM (PEM) electrolytic cell, which comprises the following steps: (1) Cutting a stainless steel metal matrix, then carrying out surface degreasing and pickling, and then carrying out soaking and corrosion processing to form micro-nano cavities on the surface of the matrix; (2) After ultrasonic cleaning the treated matrix, electroplating a Ni and Ni-Cr composite layer on the surface, then attaching a slurry formed by conductive carbon black and epoxy resin, then solidifying, carbonizing and alloying to form a gradient coating, finally carrying out composite rolling and stamping, and cleaning to obtain the PEM electrolytic cell anode bipolar plate. The anode bipolar plate obtained by the invention has higher mechanical strength, oxidation resistance, corrosion resistance and excellent electric conduction and hydrophobicity, and is suitable for bipolar plates of proton exchange membrane electrolytic cells in strong oxidizing environments.
Description
Technical Field
The invention belongs to the field of PEM water electrolysis hydrogen production, and particularly relates to a preparation method of an anode bipolar plate of a PEM electrolytic tank.
Background
At present, PEM water electrolysis hydrogen production technology has been applied to the fields of hydrogen production on site in a hydrogen station, renewable energy source water electrolysis hydrogen production such as wind power, energy storage and the like, and gradually popularized. The cell costs have been reduced by 40% over the last 5 years, but the high investment and operating costs remain a significant challenge to PEM water electrolysis hydrogen production. The PEM water electrolysis hydrogen production is different from alkaline water electrolysis hydrogen production, and the PEM water electrolysis hydrogen production adopts a perfluorinated sulfonic acid proton exchange membrane with good chemical stability, proton conductivity and gas separation as a solid electrolyte to replace an asbestos membrane, so that electron transfer can be effectively prevented, and the safety of an electrolytic cell is improved. The main components of the PEM water electrolyzer are a proton exchange membrane, a cathode-anode catalytic layer, a cathode-anode gas diffusion layer, a cathode-anode bipolar plate and the like from inside to outside.
The PEM water electrolyzer voltage is higher than that of a fuel cell and the anode plate requires extremely high oxidation resistance and conductivity. The traditional stainless steel material can not meet the requirements, and constructing a multi-gradient coating is an effective way for prolonging the service life of the anode bipolar plate.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an anode bipolar plate of a PEM (proton exchange membrane) electrolytic tank, wherein the anode bipolar plate obtained by the method has higher mechanical strength, oxidation resistance, corrosion resistance and excellent electric conduction and hydrophobicity, and is suitable for a proton exchange membrane in a strong oxidizing environment.
The invention provides a preparation method of an anode bipolar plate of a PEM (PEM) electrolytic cell, which comprises the following steps:
(1) Cutting a stainless steel metal matrix, then carrying out surface degreasing and pickling, and then carrying out soaking and corrosion processing to form micro-nano cavities on the surface of the matrix;
(2) After ultrasonic cleaning the treated matrix, electroplating a Ni and Ni-Cr composite layer on the surface, then attaching a slurry formed by conductive carbon black and epoxy resin, then solidifying, carbonizing and alloying to form a gradient coating, finally carrying out composite rolling and stamping, and cleaning to obtain the PEM electrolytic cell anode bipolar plate.
The cutting requirements in the step (1) are as follows: the elongation is more than or equal to 10 percent, and the cupping value is more than or equal to 6.5mm so as to ensure the subsequent punching performance.
The processing liquid used for the soaking corrosion processing in the step (1) comprises the following components: 0.3-0.6mol/L FeCl 3 ，0.3-0.6mol/L NaFAnd 1-2mol/L NaOH; the processing time is 0.1-2h.
The depth of the micro-nano cavity in the step (1) is 10-20 mu m.
The thickness of the Ni coating in the step (2) is 10 mu m, and the thickness of the Ni-Cr composite layer is 15-20 mu m.
The thickness of the slurry formed by the suspended conductive carbon black and the epoxy resin is 10-15 mu m, the component ratio is 80% of the conductive carbon black, 20% of the epoxy resin, and alcohol is used as a solvent for uniform mixing.
The curing temperature in the step (2) is 180-200 ℃ and the curing time is 20-40min.
The carbonization temperature in the step (2) is 600-700 ℃, the carbonization time is 3-6h, and nitrogen is introduced.
The gradient coating in the step (2) is a C-CrC (CrCN) -NiCr-Ni-matrix coating. Nitrogen, which is finally dissociated by the atmosphere and between Cr metal and carbon, diffuses into CrC (CrCN) during the subsequent heat treatment. The gradient coating is beneficial to improving the service life, oxidation resistance and conductivity of the anode bipolar plate, meanwhile, graphite carbon on the surface has excellent hydrophobicity and conductivity, and even if the carbon is oxidized at high voltage, a CrC (CrCN) ceramic phase can realize high conductivity and high oxidation resistance.
The composite rolling temperature in the step (2) is 550-650 ℃, the time is 2-3h, and the rolling deformation degree is 5% -8%.
The cleaning in the step (2) is as follows: and (3) punching the flow channel, and cleaning the carbon micro powder particles on the surface.
Advantageous effects
The anode bipolar plate obtained by the invention has higher mechanical strength, oxidation resistance, corrosion resistance and excellent electric conduction and hydrophobicity, and is suitable for PEM electrolytic cells in strong oxidizing environments.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.3mol/L FeCl 3 0.3mol/L NaF and 1mol/L NaOH; the processing time is 0.2h, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the substrate;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a slurry (conductive carbon black 80% and epoxy resin 20%) composed of conductive carbon black and epoxy resin was attached to the surface by a squeegee to a thickness of 10 μm. And then curing for 30min at 180 ℃, carbonizing for 2h at 700 ℃ in nitrogen atmosphere to form a C-CrC (CrCN) -Cr-Ni-matrix coating, heating at 550 ℃ for 2h under nitrogen protection, carrying out compound rolling to obtain a bipolar plate with the rolling deformation degree of 5%, and the thickness of the bipolar plate being 2mm, punching a runner on the obtained compound coating sample, and cleaning carbon micro powder particles on the surface to obtain the anode bipolar plate of the PEM electrolytic tank.
(3) The performance of the prepared anode bipolar plate of the PEM electrolytic tank is tested by adopting a four-probe resistance tester, the direct reading test conductivity is realized, the corrosion current density is tested by adopting a three-electrode test, and the corrosion medium is 0.5M H 2 SO 4 +5PPMHF, test temperature 70 ℃, service life greater than 5800h, conductivity 110S/cm, corrosion current density 0.15 μA/cm 2 。
Example 2
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.6mol/L FeCl 3 0.6mol/L NaF and 2mol/L NaOH; the processing time is 0.1h, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the substrate;
(2) After ultrasonic cleaning of the treated matrix, electroplating a Ni-Cr composite layer with the thickness of 10 mu m and 20 mu m on the surface, hanging conductive carbon black and epoxy resin to form slurry (80% of conductive carbon black and 20% of epoxy resin) with the thickness of 15 mu m by adopting a scraping plate, curing for 40min at 180 ℃, carbonizing for 3h at 700 ℃ and forming a C-CrC (CrCN) -Cr-Ni-matrix coating in nitrogen atmosphere, heating at 650 ℃ for 2h under nitrogen protection, carrying out compound rolling, wherein the rolling deformation degree is 5%, and finally the thickness of a bipolar plate is 2mm, punching a runner on the obtained composite coating sample, and cleaning carbon micro powder particles on the surface to finally obtain the PEM electrolytic tank anode bipolar plate.
(3) The performance of the anode bipolar plate of the PEM electrolyzer was tested by the same method as in example 1, with a service life of more than 7000h, a conductivity of 125S/cm and a corrosion current density of 0.12. Mu.A/cm 2 。
Example 3
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.4mol/L FeCl 3 0.4mol/L NaF and 2mol/L NaOH; the processing time is 10min, so that micro-nano holes with the diameter of 10 mu m are formed on the surface of the substrate;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a slurry (conductive carbon black 80% and epoxy resin 20%) composed of conductive carbon black and epoxy resin was pasted with a blade to a thickness of 12 μm. And then curing for 30min at 200 ℃, carbonizing for 3h at 650 ℃ to form a C-CrC (CrCN) -Cr-Ni-matrix coating, heating at 550 ℃ for 3h under nitrogen protection, carrying out composite rolling to obtain a bipolar plate with the rolling deformation degree of 8%, and the thickness of 2mm, punching a runner on the obtained composite coating sample, and cleaning carbon micro powder particles on the surface to obtain the anode bipolar plate of the PEM electrolytic tank.
(3) The performance of the anode bipolar plate of the PEM electrolytic cell prepared was tested by the same method as in example 1, with a service life of greater than 6500h, a conductivity of 118S/cm and a corrosion current density of 0.13. Mu.A/cm 2 。
Example 4
(1) For stainless steel metalCutting the matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.5mol/L FeCl 3 0.5mol/L NaF and 1.5mol/L NaOH; the processing time is 20min, so that micro-nano holes with the diameter of 20 mu m are formed on the surface of the matrix;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a paste (conductive carbon black 80%, epoxy resin 20%) composed of conductive carbon black and epoxy resin was pasted with a squeegee to a thickness of 15 μm. And then curing for 40min at 200 ℃, carbonizing for 4h at 700 ℃ to form a C-CrC (CrCN) -Cr-Ni-matrix coating, heating at 650 ℃ for 3h under nitrogen protection, carrying out compound rolling to obtain a bipolar plate with the rolling deformation degree of 6%, and the thickness of the bipolar plate being 2mm, punching a runner on the obtained compound coating sample, and cleaning carbon micro powder particles on the surface to obtain the anode bipolar plate of the PEM electrolytic tank.
(3) The performance of the prepared anode bipolar plate of the PEM electrolytic cell is tested, the service life is longer than 8000h, the conductivity is 127S/cm, and the corrosion current density is 0.09 mu A/cm 2 。
Example 5
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.6mol/L FeCl 3 0.3mol/L NaF and 1mol/L NaOH; the processing time is 15min, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the matrix;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 15 μm was electroplated on the surface, and a slurry (conductive carbon black 80% and epoxy resin 20%) composed of conductive carbon black and epoxy resin was pasted with a squeegee to a thickness of 10 μm. And then curing for 25min at 180 ℃, carbonizing for 3h at 600 ℃ to form a C-CrC (CrCN) -Cr-Ni-matrix coating, heating at 650 ℃ for 2h under nitrogen protection, carrying out composite rolling to obtain a bipolar plate with the rolling deformation degree of 7%, and the thickness of 2mm, punching a runner on the obtained composite coating sample, and cleaning carbon micro powder particles on the surface to obtain the anode bipolar plate of the PEM electrolytic tank.
(3) The performance of the prepared anode bipolar plate of the PEM electrolytic cell has the service life of more than 6700h, the conductivity of 115S/cm and the corrosion current density of 0.13 mu A/cm 2 。
Example 6
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.4mol/L FeCl 3 0.5mol/L NaF and 1.5mol/L NaOH; the processing time is 40min, so that micro-nano holes with the diameter of 20 mu m are formed on the surface of the matrix;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a paste (conductive carbon black 80%, epoxy resin 20%) composed of conductive carbon black and epoxy resin was pasted with a squeegee to a thickness of 15 μm. And then curing for 30min at 200 ℃, carbonizing for 3h at 600 ℃ under nitrogen protection to form a C-CrC (CrCN) -Cr-Ni-matrix coating, heating at 650 ℃ under nitrogen protection for 2h, carrying out composite rolling to obtain a bipolar plate with the rolling deformation degree of 5%, and the thickness of the bipolar plate being 2mm, punching a runner on the obtained composite coating sample, and cleaning carbon micro powder particles on the surface to obtain the anode bipolar plate of the PEM electrolytic tank.
(3) The performance of the anode bipolar plate of the PEM electrolytic cell prepared was tested by the same method as in example 1, with a service life of greater than 6900h, a conductivity of 121S/cm and a corrosion current density of 0.12. Mu.A/cm 2 。
Comparative example 1
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.3mol/L FeCl 3 0.3mol/L NaF and 1mol/L NaOH; the processing time is 0.2h, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the substrate;
(2) After the above-treated substrate was ultrasonically cleaned, a 10 μm and 10 μm Ni/Ni-Cr composite layer was electroplated on the surface, and the substrate was heated under nitrogen protection at 550℃for 2 hours, and subjected to clad rolling with a rolling deformation degree of 5%. Due to the lack of a curing process, the binding force between the coating and the substrate is poor, edge cracking occurs in the rolling process, the subsequent stamping processing is affected, and after an additional cutting process is added, a bipolar plate sample piece with the thickness of 2mm is obtained, but in the process of stamping a flow channel on the sample piece, the flow channel with high dimensional accuracy is difficult to obtain due to different deformability, large strain gradient difference and poor deformation coordination of the Ni-Cr composite layer and the stainless steel substrate.
(3) The performance of the anode bipolar plate of the PEM electrolytic cell was tested by the same method as in example 1, with a service life of less than 3500h and a corrosion current density of 1.2. Mu.A/cm 2 The conductivity was 60S/cm. The above properties are difficult to meet the use requirements of industrial electrolytic tanks.
Comparative example 2
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10%, and the cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.3mol/L FeCl 3 0.3mol/L NaF and 1mol/L NaOH; the processing time is 0.2h, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the substrate;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a slurry (conductive carbon black 80% and epoxy resin 20%) composed of conductive carbon black and epoxy resin was attached to the surface by a squeegee to a thickness of 10 μm. And then solidifying for 30min at 300 ℃, carbonizing for 2h at 700 ℃, heating at 550 ℃ under nitrogen atmosphere, carrying out compound rolling, wherein the rolling deformation degree is 5%, the thickness of the bipolar plate is 2mm, punching a runner on the obtained compound coating sample, and cleaning carbon micro powder particles on the surface to obtain the PEM electrolytic cell anode bipolar plate.
(3) The performance of the prepared anode bipolar plate of the PEM electrolytic cell is tested, the service life is longer than 5000h, the conductivity is 130S/cm, and the corrosion current density is 0.12 mu A/cm 2 But PEM electrolyser anode bipolar plates become fragile.
Comparative example 3
(1) Cutting the stainless steel metal matrix, wherein the elongation is more than or equal to 10The cupping value is more than or equal to 6.5mm; then carrying out surface degreasing and acid washing, and then carrying out soaking and corrosion processing, wherein the composition of the processing liquid is as follows: 0.3mol/L FeCl 3 0.3mol/L NaF and 1mol/L NaOH; the processing time is 0.2h, so that micro-nano holes with the thickness of 15 mu m are formed on the surface of the substrate;
(2) After the above-treated substrate was ultrasonically cleaned, a Ni-Ni composite layer of 10 μm and 20 μm was electroplated on the surface, and a slurry (conductive carbon black 80% and epoxy resin 20%) composed of conductive carbon black and epoxy resin was attached to the surface by a squeegee to a thickness of 10 μm. And then curing for 30min at 180 ℃, carbonizing for 2h at 800 ℃, heating at 550 ℃ under nitrogen atmosphere, performing composite rolling, wherein the rolling deformation degree is 5%, the thickness of the bipolar plate is 2mm, punching a runner on the obtained composite coating sample, and cleaning carbon micro powder particles on the surface to obtain the PEM electrolytic cell anode bipolar plate.
(3) Performance test is carried out on the anode bipolar plate of the PEM electrolytic tank, the service life is longer than 4500h, the conductivity is 143S/cm, and the corrosion current density is 0.11 mu A/cm 2 But PEM electrolyser anode bipolar plates become fragile.
Claims (9)
1. A method for preparing an anode bipolar plate of a PEM electrolyzer, comprising:
(1) Cutting a stainless steel metal matrix, then carrying out surface degreasing and pickling, and then carrying out soaking and corrosion processing to form micro-nano cavities on the surface of the matrix; wherein, the processing liquid used for the soaking corrosion processing comprises the following components: 0.3-0.6mol/L FeCl 3 0.3-0.6mol/L NaF and 1-2mol/L NaOH;
(2) After ultrasonic cleaning of the treated matrix, electroplating a Ni and Ni-Cr composite layer on the surface, then hanging a slurry formed by conductive carbon black and epoxy resin, then solidifying, carbonizing and alloying to form a gradient coating, finally carrying out composite rolling and stamping, and cleaning to obtain a PEM electrolytic cell anode bipolar plate; wherein the thickness of the Ni-Cr composite layer is 15-20 mu m; the curing temperature is 180-200 ℃; the carbonization temperature is 600-700 ℃ and nitrogen is introduced; the gradient coating is a C-CrC (CrCN) -NiCr-Ni-matrix coating; wherein CrC (CrCN) is formed by diffusion of free nitrogen between Cr metal and carbon and in the atmosphere during subsequent heat treatment.
2. The method of manufacturing according to claim 1, characterized in that: the cutting requirements in the step (1) are as follows: the elongation is more than or equal to 10 percent, and the cupping value is more than or equal to 6.5mm.
3. The method of manufacturing according to claim 1, characterized in that: the soaking corrosion processing time in the step (1) is 0.1-2h.
4. The method of manufacturing according to claim 1, characterized in that: the depth of the micro-nano cavity in the step (1) is 10-20 mu m.
5. The method of manufacturing according to claim 1, characterized in that: the thickness of the Ni coating in the step (2) is 10 mu m; the thickness of slurry formed by the suspended conductive carbon black and the epoxy resin is 10-15 mu m, the composition ratio of the suspended conductive carbon black to the epoxy resin is 80 percent, the epoxy resin is 20 percent, and alcohol is used as a solvent for uniform mixing.
6. The method of manufacturing according to claim 1, characterized in that: the curing time in the step (2) is 20-40min.
7. The method of manufacturing according to claim 1, characterized in that: and (3) carbonizing time in the step (2) is 3-6h.
8. The method of manufacturing according to claim 1, characterized in that: the composite rolling temperature in the step (2) is 550-650 ℃, the time is 2-3h, and the rolling deformation degree is 5% -8%.
9. The method of manufacturing according to claim 1, characterized in that: the cleaning in the step (2) is as follows: and (3) punching the flow channel, and cleaning the carbon micro powder particles on the surface.
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| WO2014081316A1 (en) * | 2012-11-21 | 2014-05-30 | Sinvent As | Bipolar plates, method and use of these plates in polymer electrolyte membrane (pem) fuel cells or other electrochemical cells |
| CN103972528A (en) * | 2014-05-30 | 2014-08-06 | 长沙理工大学 | Preparation method of metal bipolar plate protective coating of proton exchange membrane fuel cell |
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| TW200518376A (en) * | 2003-11-18 | 2005-06-01 | Univ Yuan Ze | Surface protection film structure of metal electrode plate for fuel battery and surface treatment method |
| US7267869B2 (en) * | 2004-07-28 | 2007-09-11 | Leo Kriksunov | Conductive corrosion-resistant coating |
| KR100839193B1 (en) * | 2008-01-21 | 2008-06-17 | 현대하이스코 주식회사 | Metallic bipolar plate having surface layer which carbon particles dispersed in the binder polymer for fuel cell and its manufacturing method |
| TW201101565A (en) * | 2009-06-19 | 2011-01-01 | Univ Yuan Ze | Method for preparing surface modification coating of stainless-steel bipolar plates |
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| WO2014081316A1 (en) * | 2012-11-21 | 2014-05-30 | Sinvent As | Bipolar plates, method and use of these plates in polymer electrolyte membrane (pem) fuel cells or other electrochemical cells |
| CN103972528A (en) * | 2014-05-30 | 2014-08-06 | 长沙理工大学 | Preparation method of metal bipolar plate protective coating of proton exchange membrane fuel cell |
| CN107170993A (en) * | 2017-05-02 | 2017-09-15 | 武汉理工大学 | A kind of method of used in proton exchange membrane fuel cell Fe Cr Ni alloys double-polar plate surface modifying processing |
| CN108411283A (en) * | 2018-02-09 | 2018-08-17 | 中南大学 | A kind of preparation method of metallic matrix/nonmetal basal body carbon composite coating or carbon conductive composite coating |
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