CN110629150B - Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof - Google Patents
Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN110629150B CN110629150B CN201810552971.5A CN201810552971A CN110629150B CN 110629150 B CN110629150 B CN 110629150B CN 201810552971 A CN201810552971 A CN 201810552971A CN 110629150 B CN110629150 B CN 110629150B
- Authority
- CN
- China
- Prior art keywords
- end plate
- ceramic
- coating
- metal
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000446 fuel Substances 0.000 title abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 94
- 239000000843 powder Substances 0.000 claims abstract description 89
- 239000011248 coating agent Substances 0.000 claims abstract description 85
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 43
- 238000007750 plasma spraying Methods 0.000 claims abstract description 41
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 38
- 238000005507 spraying Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 13
- 238000007789 sealing Methods 0.000 claims description 39
- 239000000919 ceramic Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229940078494 nickel acetate Drugs 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 16
- 229910000838 Al alloy Inorganic materials 0.000 claims description 15
- 238000005488 sandblasting Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005422 blasting Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000004482 other powder Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 12
- 238000005237 degreasing agent Methods 0.000 claims 1
- 239000013527 degreasing agent Substances 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 238000007751 thermal spraying Methods 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 35
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000010432 diamond Substances 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a ceramic coating on the surface of a metal end plate of a fuel cell and a preparation method thereof. The preparation method comprises the steps of carrying out atmospheric plasma spraying treatment on the metal end plate; the raw material of the atmospheric plasma spraying is selected from ZrO2、Al2O3AlN and Si3N4One or more of the powders; the atmosphere plasma spraying conditions are that the spraying distance is 60-120 mm, the spraying power is 30-60 kW, the powder feeding rate is 20-45 g/min, and the powder feeding angle is 10-60 degrees. The ceramic coating prepared on the surface of the metal end plate by adopting the thermal spraying technology can further improve the corrosion resistance and the wear resistance of the end plate, is beneficial to preparing a high-performance fuel cell, is beneficial to designing a proper end plate coating according to actual requirements, and is suitable for the fuel cell under multiple working conditions.
Description
Technical Field
The invention relates to a ceramic coating on the surface of a metal end plate of a fuel cell and a preparation method thereof.
Background
The proton exchange membrane fuel cell takes hydrogen as fuel, chemical energy is converted into electric energy through an electrochemical method, and a reaction product is water, so that the proton exchange membrane fuel cell has no pollution to the environment. The proton exchange membrane fuel cell has the advantages of high energy conversion efficiency (50-80%), quick start at low temperature, high power density and the like, can be applied to new energy automobiles, distributed energy sources, portable small power sources and the like, and is widely concerned by governments, energy sources and automobile enterprises at present.
The electric pile is the core module of the proton exchange membrane fuel cell generating system, and the conventional fuel cell mainly comprises a membrane electrode, an anode plate, a cathode plate, an insulation plate, a collector plate, an end plate, a sealing layer and other parts. The end plate is one of the key components of the stack, and is connected with each battery assembly through the fastening component to form a stable stack structure, and the pretightening force is uniformly distributed to each assembly in the stack, so that the end plate material needs to have certain strength. Since the pem fuel cell generally operates at a temperature of 80 ℃, the end plates need to maintain a certain strength at this temperature, and softening deformation cannot occur. In addition, in the operation process of the fuel cell, the air inlet needs to be humidified, and water generated by reaction is discharged along with gas, so that high-humidity gas or gas-liquid two-phase flow is arranged at the inlet and the outlet, the interior of the cell is weakly acidic, and the end plate is required to be resistant to acid corrosion. In order to increase the weight specific power and the volume specific power of the entire stack, the end plates need to be as low in density as possible while maintaining sufficient strength. Therefore, the end plate applicable to the proton exchange membrane fuel cell stack is required to have properties such as good insulation, corrosion resistance, low density, and high strength.
The end plate materials commonly used at present mainly include metals, engineering plastics and polysulfone materials, wherein metal materials such as metal titanium plates and stainless steel plates have high strength, but an insulating plate (engineering plastics) needs to be added between the current collecting plate and the end plate, which complicates the fuel cell system. The end plates made of engineering plastics and polysulfone materials are not good enough in thermal stability, are easy to deform at the operating temperature of the battery pack, and are usually heavy in design due to the fact that the end plates made of the materials need to keep certain strength.
The existing proton exchange membrane fuel cell has the following problems:
1. the collector plates and end plates of a pem fuel cell stack are made of metal materials, and an insulating plate needs to be added between the collector plates and the end plates, so that the number of parts is increased, and the sealing difficulty and the assembly complexity of the stack are increased.
2. By adopting the existing anodic oxidation process with constant current density, the coating strength can not meet the requirement of a high-performance fuel cell, and the types of the oxidation film materials are greatly limited. The existing constant-voltage anodic oxidation process is adopted, and then the anode is sealed in boiling water, so that defects exist in an oxide layer, corrosion can occur in the running process of a battery pack, and the requirement of a fuel cell on the performance of an end plate cannot be met.
3. The metal material is adopted as the material of the end plate of the fuel cell, because the end plate is required to be provided with fluid through holes, fluid enters each single cell through the through holes on the collector plate, the plating layer of the collector plate is corroded or falls off due to the fact that the fluid erodes the through holes of the collector plate for a long time, the surface of the collector plate is corroded, metal ions in the collector plate can be brought into a cathode layer and an anode catalyst layer of the fuel cell in a large amount, and therefore the catalyst is poisoned, the performance of the catalyst is affected, and the structure of the end plate of the existing proton membrane fuel cell is shown in figure 1.
4. The proton exchange membrane fuel cell stack usually only applies one-time pre-pressing force during the assembly process, which easily causes the fracture of the bipolar plate and the damage of the coating on the surface of the end plate.
Disclosure of Invention
The invention provides a ceramic coating on the surface of a metal end plate of a fuel cell and a preparation method thereof, aiming at solving the problems of complex structure of a fuel cell stack, poor abrasion resistance, corrosion resistance and strength of a cell end plate and the like in the prior art. The ceramic coating prepared on the surface of the metal end plate by adopting the thermal spraying technology can further improve the corrosion resistance and the wear resistance of the end plate, is beneficial to preparing a high-performance fuel cell, is beneficial to designing a proper end plate coating according to actual requirements, and is suitable for the fuel cell under multiple working conditions.
The invention provides a preparation method of a metal end plate ceramic coating, which comprises the following steps of carrying out atmospheric plasma spraying treatment on a metal end plate;
the raw material of the atmospheric plasma spraying is selected from ZrO2、Al2O3AlN and Si3N4One or more kinds of powder;
the atmosphere plasma spraying conditions comprise that the spraying distance is 60-120 mm, the spraying power is 30-60 kW, the powder feeding rate is 20-45 g/min, and the powder feeding angle (theta) is 10-60 degrees.
In the present invention, it is preferable that the raw material for the atmospheric plasma spraying contains Al2O3Powder; more preferably, the raw material of the atmospheric plasma spraying is any one of the following three combinations: ZrO (ZrO)2And Al2O3Powder of AlN and Al2O3Powder of, or of, Si3N4And Al2O3Powder; most preferably, the raw materials for the atmospheric plasma spraying are AlN and Al2O3And (3) powder.
In the present invention, when the raw material for the atmospheric plasma spraying contains Al2O3Powder and other one or more kinds of powder, the Al2O3The mass ratio of the powder to the other powder or the other powders is preferably 8:1 to 12:1, and more preferably 9: 1.
In the present invention, the particle size of the powder is preferably 10 to 50 μm, such as 10 to 40 μm, 15 to 45 μm or 15 to 35 μm.
In the present invention, the bulk density of the powder is preferably 1 to 3g/cm3For example, 2.00 to 2.32g/cm3。
In the present invention, the raw material for the atmospheric plasma spraying is available from Shitaceae chemical trade (Shanghai) Co., Ltd., for example, the ZrO2The powder may be AMPERIT831, Al2O3The powder can be AMPERIT740, the AlN powder can be AMPERIT105, and the Si3N4The powder may be available in AMPERIT 587.
In the present invention, the spraying distance is preferably 70 to 90mm, for example, 70mm, 80mm or 90 mm.
In the present invention, the spraying power is preferably 60 kW.
In the present invention, the powder feeding rate is preferably 40 g/min.
In the present invention, the powder feeding angle is preferably 45 to 50 °.
In the present invention, the metal end plate is preferably an aluminum alloy end plate.
Wherein the elastic modulus of the aluminum alloy end plate is preferably 70 GPa.
Wherein the poisson ratio of the aluminum alloy end plate is preferably 0.33.
Wherein, the tensile strength of the aluminum alloy end plate is preferably 100-300 MPa.
The aluminum alloy end plate preferably has an elastic modulus of 70GPa, a Poisson ratio of 0.33 and a tensile strength of 100-300 MPa.
In the invention, the metal end plate can be subjected to sand blasting treatment and preheating treatment before being subjected to atmospheric plasma spraying.
Wherein, the sand blasting treatment can be the conventional sand blasting treatment in the field, and preferably is carried out on the metal end plate by selecting 10-25 meshes of corundum sand under the air pressure of 0.5-1 MPa. After the sand blasting treatment, the surface cleanliness of the metal end plate is preferably higher than grade Sa 2.
The preheating temperature may be a conventional temperature in the art, preferably 80 to 200 ℃, and more preferably 100 ℃.
Wherein, cleaning treatment can be carried out before the sand blasting treatment and/or after the sand blasting treatment.
The cleaning treatment before the blasting treatment is preferably alcohol cleaning.
The cleaning treatment after the sand blasting treatment is preferably:
selecting 15-35 g/L NaOH and 20-30 g/L NaCO3The mixed solution is used as an oil removing agent, and the metal end plate is treated for 1-5 min at the temperature of 20-45 ℃; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1 to 5min at the temperature of 20 to 25 ℃. The NaOH and the NaCO3The mass ratio of (A) is preferably 1 (2-5), more preferably 1: 3.
Or treating the metal end plate by using a neutral organic solvent at the temperature of 20-25 ℃ for 1-5 min; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1 to 5min at the temperature of 20 to 25 ℃. The neutral organic solvent is preferably acetone.
In the invention, after the metal end plate is subjected to atmospheric plasma spraying, hole sealing treatment can be performed according to the conventional method in the field. The sealing treatment may be a treatment method conventional in the art, for example, the metal end plate after being subjected to atmospheric plasma spraying may be mixed with a sealing liquid.
The sealing liquid can be a sealing liquid conventional in the art, such as a potassium dichromate solution, a nickel acetate solution, a zirconia sol, or an alumina sol.
The potassium dichromate solution is available from Shanghai Aladdin Biotechnology, Inc. with a specification of 1/24mol/L (0.25N). The concentration of the potassium dichromate solution is preferably 40-75 g/L.
The nickel acetate solution can be prepared by a conventional method in the field, for example, acetic acid, nickel acetate and distilled water are mixed according to the mass ratio of (1-3): 3-5): 20; the concentration of nickel ions in the nickel acetate solution is 1-3 g/L, and the concentration of acetic acid in the nickel acetate solution is 0.017-0.17 g/L. The mass ratio of the acetic acid, the nickel acetate and the distilled water is preferably 1:5: 20. The nickel acetate can be industrial nickel acetate ((CH) from Yongyun Industrial chemical industries, Ltd of Foshan3COO)2Ni·4H2O). The acetic acid may be industrial acetic acid (CH) available from Dow chemical Co., Ltd3COOH)。
The zirconia sol or the alumina sol can be prepared by adopting a conventional alkoxide hydrolysis method in the field, for example, zirconia or alumina, a solvent, a stabilizer, deionized water and nitric acid are mixed, and the volume ratio of the solvent to the stabilizer to the deionized water to the nitric acid is 1 (20-50) to 1: 1. The zirconia or alumina is available from Shitaceae chemical trade (Shanghai) Co., Ltd., for example, the zirconia (ZrO)2) The powder of (A) may be AMPERIT831, the aluminum oxide (Al)2O3) The powder grade of (a) may be AMPERIT 740. The solvent is preferably propanol. The stabilizer is preferably acetylacetone. The volume ratio of the solvent, the stabilizer, the deionized water and the nitric acid is preferably 1 (25-45): 1:1, more preferably 1:25:1:1 or 1:45:1: 1. The temperature of the mixing may be normal temperature, typically 25 ℃.
When the hole sealing liquid is a potassium dichromate solution or a nickel acetate solution, the pH of the hole sealing liquid is preferably 5-7, the mixing temperature in hole sealing treatment is preferably 80-95 ℃, and the mixing time in hole sealing treatment is preferably 20-45 min.
When the hole sealing liquid is zirconia sol or alumina sol, preferably, the metal end plate is immersed into the hole sealing liquid, the metal end plate is pulled to obtain a metal end plate coated with the hole sealing liquid on the surface, and the metal end plate coated with the hole sealing liquid on the surface is subjected to heat treatment. The pulling speed is preferably 0.1 to 0.5 mm/s. The heat treatment may be performed in a muffle furnace. The temperature of the heat treatment is preferably 100 to 300 ℃. The time of the heat treatment is preferably 10 to 30 min. The steps of immersing, pulling and heat treating are preferably repeated 5-30 times.
In a preferred embodiment of the invention, the raw material for the atmospheric plasma spraying is selected from ZrO2And Al2O3Powder of the ZrO2Powder and the Al2O3The mass ratio of the powder is 1: 9; the atmosphere plasma spraying conditions comprise that the spraying distance is 70mm, the spraying power is 40kW, the powder feeding rate is 40g/min, and the powder feeding angle is 45-50 degrees.
In a preferred embodiment of the present invention, the raw material for the atmospheric plasma spraying is selected from AlN and Al2O3Powder, the AlN powder and the Al2O3The mass ratio of the powder is 1: 9; the atmosphere plasma spraying conditions comprise that the spraying distance is 80mm, the spraying power is 40kW, the powder feeding rate is 40g/min, and the powder feeding angle is 45-50 degrees.
In a preferred embodiment of the present invention, the raw material for the atmospheric plasma spraying is selected from Si3N4And Al2O3Powder of said Si3N4Powder and the Al2O3The mass ratio of the powder is 1: 9; the atmosphere plasma spraying conditions comprise that the spraying distance is 90mm, the spraying power is 40kW, the powder feeding rate is 40g/min, and the powder feeding angle is 45-50 degrees.
The invention also provides a metal end plate ceramic coating prepared by the preparation method.
The thickness of the metal end plate ceramic coating is preferably 10 to 100 μm, and more preferably 40 to 50 μm.
The porosity of the metal end plate ceramic coating is preferably 1 to 10%, more preferably 5 to 10%, and the percentage is the percentage of the pore volume in the metal end plate ceramic coating to the total volume of the metal end plate ceramic coating.
Preferably, the metal end plate ceramic coating includes a ceramic layer and a microporous layer, one side of the ceramic layer is adjacent to the metal end plate, the other side of the ceramic layer is adjacent to the microporous layer, the ceramic layer has a columnar crystal structure, and the ceramic layer and the microporous layer are parallel to each other.
The surface of the metal end plate ceramic coating is preferably also provided with a hole sealing layer. The thickness of the hole sealing layer is preferably 1 to 20 μm. As known to those skilled in the art, the surface of the ceramic coating of the metal end plate refers to the side covered with the ceramic coating.
Preferably, the thickness of the metal end plate ceramic coating is 10-100 μm, the bonding strength is greater than 100MPa, the porosity is 1-10%, the percentage is the percentage of the pore volume in the metal end plate ceramic coating to the total volume of the metal end plate ceramic coating, and the elastic modulus is 50-100 GPa.
The invention adopts a multifunctional micro-mechanical testing machine to test the bonding strength and adopts SEM to test the porosity.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. according to the invention, the aluminum alloy is used as the end plate, the end plate coating is prepared by adopting the atmospheric plasma spraying, the insulating layer is formed on the surface of the end plate in situ, the insulating layer is not required to be additionally arranged between the current collecting plate and the end plate, the end plate and the current collecting plate are integrated, the galvanic pile structure is simplified, and the requirement of light weight is met.
2. The thermal spraying technology is adopted to prepare various insulating ceramic coatings on the surface of the aluminum alloy end plate, the method is suitable for designing the fuel cell stack under multiple working conditions, the ceramic coating structure is designed into a compact columnar crystal and parallel microporous layer, the corrosion resistance, wear resistance and mechanical strength of the coating are improved, and the damage to the surface of the end plate in the stack assembly process is effectively avoided.
3. Select ZrO2、Al2O3、AlN、Si3N4In the two methods, the composite coating is prepared by adopting a thermal spraying technology, so that the corrosion resistance and the mechanical property of the coating can be further improved.
4. The alumina ceramic prepared by the thermal spraying process has good insulating property and higher hardness, and can be applied to a coating material on the surface of an end plate of a fuel cell, but the overall hardness of the coating is influenced by the ceramic coating in a spraying state because the ceramic coating contains pores in different proportions. By using Al2O3The ceramic powder is mixed with other ceramic powder, and a composite coating is prepared on the surface of the fuel cell end plate, so that the two ceramic particles are fused together, and the bonding strength and the compactness of the coating can be further improved.
5. The composite coating prepared by the thermal spraying process has the characteristics of a single coating, and the combination of the composite coating and the single coating has an effect of inhibiting the poor performance of the coating. For example, AlN and Al are used2O3The corrosion resistance of the coating prepared from the powder is better than that of AlN, and the AlN can inhibit alpha-Al2O3To gamma-Al2O3Transformation, thereby further improving the corrosion resistance of the coating; using ZrO2And Al2O3The coating prepared from the powder fully utilizes Al2O3The compactness of the coating can effectively prevent fluid from permeating the coating and improve the corrosion resistance; by using Si3N4And Al2O3The strength of the coating prepared from the powder is superior to that of the coating prepared from single Al2O3Coating due to Si3N4Has the function of refining grains and can react with Al under certain temperature and corrosive environment2O3The reaction forms fibrous silicate, which can relieve tensile stress and inhibit crack growth.
Drawings
Fig. 1 is a schematic structural diagram of an end plate of a proton membrane fuel cell, wherein (i) the end plate of the fuel cell and (ii) a current collecting plate.
Fig. 2 is a schematic diagram of a thermal spraying apparatus, in which plasma gas + current, cathode, water-cooled anode, coating, insulator, powder port, metal end plate, and θ is a powder feeding angle in atmospheric plasma spraying.
FIG. 3 is a schematic diagram of a ceramic coated end plate for thermal spraying a metal end plate, in which a hole sealing layer, a microporous layer, a ceramic layer, and a metal end plate are provided.
Fig. 4 shows the results of the bonding force test of the ceramic coating of the metal end plate of example 1.
Fig. 5 shows the results of the adhesion test of the ceramic coating of the metal end plate of example 2.
Fig. 6 shows the results of the adhesion test of the ceramic coating of the metal end plate of example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the thermal spray apparatus is shown in FIG. 2. In the following examples, the atmospheric plasma thermal spray apparatus used was a MultiCoat plasma spray system of the europe incorporated.
In the following embodiments, the elastic modulus of the aluminum alloy end plate is 70GPa, the Poisson ratio is 0.33, and the tensile strength is 100-300 MPa.
Example 1
Selecting aluminum alloy as a metal end plate, cleaning the surface of the end plate by using alcohol, and performing sand blasting treatment on the surface of the end plate by using 20-mesh corundum sand under the pressure of 0.5 MPa. After sand blasting, selecting 15-35 g/L NaOH and 20-30 g/L NaCO3The mixed solution of (A) is used as an oil removing agent, NaOH and NaCO3The mass ratio of the metal end plate to the metal end plate is 1:3, and the metal end plate is treated at the temperature of 20-45 ℃ for 1-5 min; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1 to 5min at the temperature of 20 to 25 ℃.
Using ZrO2And Al2O3The powder is a raw material for atmospheric plasma spraying, the mass ratio of the powder to the powder is 1:9, the particle size is controlled to be 10-40 mu m, and the apparent density is 2.00-2.32 g/cm3The atmospheric plasma spraying condition is that the spraying distance is 70mm, the spraying power is 40kW, the powder feeding rate is 40g/min, the powder feeding angle is 45-50 degrees, and the end plate is pre-sprayedThe hot temperature was 100 ℃.
The hole sealing treatment is carried out by immersing the end plate in zirconia sol, coating the zirconia sol on the surface of the end plate, then pulling the end plate, and carrying out heat treatment, wherein the zirconia sol (ZrO)2Purchased from Shantai chemical trade (Shanghai) Co., Ltd., and having a powder number of AMPERIT831), the catalyst is prepared by an alkoxide hydrolysis method, propanol is used as a solvent, acetylacetone is used as a stabilizer, the volume ratio of the propanol to the acetylacetone to deionized water to nitric acid is 1:25:1:1, and the catalyst is obtained by hydrolysis at normal temperature. Controlling the pulling speed to be 0.3mm/s, carrying out heat treatment in a muffle furnace at 150 ℃ for 25min after single pulling, and completely sealing the coating after repeating 30 times of immersion pulling heat treatment operation. The prepared coating is shown in figure 3 and comprises a hole sealing layer, a micro-hole layer, a ceramic layer and a metal end plate.
In the embodiment, a HXS-1000AKY digital display hardness tester is selected to test the hardness of the end plate coating, the pressure head of the testing equipment is a diamond regular quadrangular pyramid, the load used for testing is 4.903N, the load retention time is 10s, 6 points which are uniformly distributed are selected from the center to the edge of the surface of the sample to be measured, and the average value of the points is taken as the microhardness value of the sample. Table 1 shows microhardness test data for the ceramic coatings of the metal end plates prepared in example 1.
TABLE 1 ZrO2+Al2O3Hardness test of coating surface
In the embodiment, a CETR UMT-4 multifunctional micromechanics testing machine is selected to test the bonding force of the end plate coating, a scratch module is adopted to test the bonding force of the coating, acoustic emission signals and tangential friction force are collected, a diamond pressure head (with the curvature of 200 mu m and the loading force of 0-200N) is selected, and the diamond pressure head linearly loads a normal load along the surface of the film until the coating falls off. When the coating is in bonding failure, the peak of the acoustic emission signal is suddenly enhanced, so that the normal load at the peak of the acoustic emission signal can be used as a primary evaluation value of the critical load. Fig. 4 shows the bonding force test results of the end plate coating of example 1, and it can be seen from the test results that the average bonding force of the end plate is 67N, and the bonding strength of the obtained coatings exceeds 100MPa calculated according to the contact surface with the diameter of the diamond joint of 0.2mm, and the coatings are coatings with high bonding strength.
The thickness of the metal end plate ceramic coating prepared in the embodiment is 40-50 μm, the porosity is 5-10%, and the percentage refers to the percentage of the pore volume in the coating to the total volume of the coating.
The coating prepared in example 1 did not peel off after testing on the fuel cell test system.
Example 2
Selecting aluminum alloy as a metal end plate, cleaning the surface of the end plate by using alcohol, and performing sand blasting treatment on the surface of the end plate by using 20-mesh corundum sand under the pressure of 0.5 MPa. After sand blasting, treating the metal end plate by using acetone, and treating for 1-5 min at 20-25 ℃; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1 to 5min at the temperature of 20 to 25 ℃.
Using AlN and Al2O3The powder is a raw material for atmospheric plasma spraying, the mass ratio of the powder to the powder is 1:9, the particle size is controlled to be 15-45 mu m, and the apparent density is 2.00-2.32 g/cm3The atmospheric plasma spraying condition is that the spraying distance is 80mm, the spraying power is 40kW, the powder feeding rate is 40g/min, the powder feeding angle is 45-50 degrees, and the preheating temperature of the end plate is 100 ℃.
The hole sealing treatment is carried out by immersing the end plate into zirconia sol, coating the sol on the surface of the end plate, then pulling the end plate, and carrying out heat treatment, wherein the zirconia sol is prepared by alkoxide hydrolysis (ZrO)2The material is obtained by taking propanol as a solvent, acetylacetone as a stabilizer, and performing hydrolysis at normal temperature, wherein the powder is obtained by taking propanol as a solvent, acetylacetone as a stabilizer, and the volume ratio of the propanol to the acetylacetone to deionized water to nitric acid is 1:45:1: 1. Controlling the pulling speed to be 0.3mm/s, carrying out heat treatment in a muffle furnace at 150 ℃ for 25min after single pulling, and completely sealing the coating after repeating 30 times of immersion pulling heat treatment operation. The resulting coating was prepared as shown in fig. 3.
The hardness test method in this example was the same as in example 1. Table 2 shows microhardness test data for the ceramic coatings of the metal end plates prepared in example 2.
TABLE 2 AlN + Al2O3Hardness test of coating surface
The bonding force of the coating in this example was measured in the same manner as in example 1. Fig. 5 shows the bonding force test results of the end plate coating of example 2, and it can be seen from the test results that the average bonding force of the end plate is 121N, and the bonding strength of the obtained coatings exceeds 100MPa calculated according to the contact surface with the diameter of the diamond joint of 0.2mm, and the coatings are coatings with high bonding strength.
The thickness of the metal end plate ceramic coating prepared in the embodiment is 40-50 μm, and the porosity is 5-10%, wherein the percentage refers to the percentage of the pore volume in the coating to the total volume of the coating.
The coating prepared in example 2 did not peel off after testing on the fuel cell test system.
Example 3
Selecting aluminum alloy as a metal end plate, cleaning the surface of the end plate by using alcohol, and performing sand blasting treatment on the surface of the end plate by using 20-mesh corundum sand under the pressure of 0.5 MPa.
By using Si3N4And Al2O3The powder is a raw material for atmospheric plasma spraying, the mass ratio of the powder to the powder is 1:9, the particle size is controlled to be 15-35 mu m, and the apparent density is 2.00-2.32 g/cm3The atmospheric plasma spraying condition is that the spraying distance is 90mm, the spraying power is 40kW, the powder feeding rate is 40g/min, the powder feeding angle is 45-50 degrees, and the preheating temperature of the end plate is 100 ℃.
The hole sealing treatment is carried out by immersing the end plate into zirconia sol, coating the sol on the surface of the end plate, then pulling the end plate, and carrying out heat treatment, wherein the zirconia sol is prepared by alkoxide hydrolysis (ZrO)2From Shitaike chemical tradeThe powder of Yishanghai Limited company is AMPERIT831), propanol is used as a solvent, acetylacetone is used as a stabilizer, the mass ratio of the propanol to the acetylacetone to deionized water to nitric acid is 1:45:1:1, and the acrylic acid-containing acrylic acid is obtained by hydrolysis at normal temperature. Controlling the pulling speed to be 0.3mm/s, carrying out heat treatment in a muffle furnace at 150 ℃ for 25min after single pulling, and completely sealing the coating after repeating 30 times of immersion pulling heat treatment operation. The resulting coating was prepared as shown in fig. 3.
The hardness test method in this example was the same as in example 1. Table 3 shows microhardness test data for the ceramic coatings of the metal end plates prepared in example 3.
TABLE 3Si4N3+Al2O3Hardness test of coating surface
The bonding force of the coating in this example was measured in the same manner as in example 1. Fig. 6 shows the bonding force test results of the end plate coating of example 3, and it can be seen from the test results that the average bonding force of the end plate is 86N, and the bonding strength of the obtained coatings exceeds 100MPa calculated according to the contact surface with the diameter of the diamond joint of 0.2mm, and the coatings are coatings with high bonding strength.
The thickness of the metal end plate ceramic coating prepared in the embodiment is 40-50 μm, and the porosity is 5-10%, wherein the percentage refers to the percentage of the pore volume in the coating to the total volume of the coating.
The coating prepared in example 3 did not peel off after testing on the fuel cell test system.
Example 4
The raw material of the atmospheric plasma spraying is ZrO2The other operating conditions were the same as in example 1.
Compared with the example 1, the coating prepared in the example 4 has short service time of the surface coating and is easy to fall off when a fuel cell test system tests.
It is known to use ZrO2And Al2O3The metal end plate ceramic coating prepared from the powder,can effectively prevent the fluid from permeating the coating and improve the corrosion resistance.
Example 5
AlN was used as a raw material for the atmospheric plasma spraying, and the other operation conditions were the same as in example 2.
Compared with the example 2, the coating prepared in the example 5 has short service time of the surface coating and is easy to fall off when a fuel cell test system tests.
It is known that AlN and Al are used2O3The corrosion resistance of the metal end plate ceramic coating prepared from the powder can be further improved.
Example 6
The raw material of the atmospheric plasma spraying is Si3N4The other operating conditions were the same as in example 3.
Compared with example 3, the coating prepared in example 6 has short service time of the surface coating when tested in a fuel cell test system, and is easy to crack.
It is known that Si is used3N4And Al2O3The metal end plate ceramic coating prepared from the powder can relieve tensile stress and inhibit crack growth of the coating.
Example 7
The raw material of the atmospheric plasma spraying is Al2O3The other operating conditions were the same as in example 1.
Al prepared in example 7 compared with example 12O3The ceramic coating has good insulating property and high hardness, and can be applied to a coating material on the surface of the fuel cell end plate, but the overall hardness of the coating is influenced by the ceramic coating in a spraying state because the ceramic coating contains pores in different proportions.
It is known that Al is used2O3The ceramic powder is mixed with other ceramic powder to prepare a composite coating on the surface of the fuel cell end plate, so that the bonding strength and the density of the ceramic coating of the metal end plate can be further improved.
Claims (28)
1. A preparation method of a metal end plate ceramic coating is characterized by comprising the following steps of carrying out atmospheric plasma spraying treatment on a metal end plate;
the raw material of the atmospheric plasma spraying is selected from ZrO2、Al2O3AlN and Si3N4One or more of the powders;
the atmospheric plasma spraying conditions are that the spraying distance is 60-120 mm, the spraying power is 30-60 kW, the powder feeding rate is 20-45 g/min, and the powder feeding angle is 10-60 degrees.
2. The method of making a ceramic coating for a metal end plate of claim 1 wherein said metal end plate is an aluminum alloy end plate;
and/or the particle size range of the powder is 10-50 mu m;
and/or the loose packing density of the powder is 1-3 g/cm3；
And/or the spraying distance is 70-90 mm;
and/or the spraying power is 60 kW;
and/or the powder feeding rate is 40 g/min;
and/or the powder feeding angle is 45-50 degrees.
3. The method of making a ceramic coating for a metal end plate of claim 2 wherein said aluminum alloy end plate has an elastic modulus of 70 Gpa;
and/or the poisson's ratio of the aluminum alloy end plate is 0.33;
and/or the tensile strength of the aluminum alloy end plate is 100-300 MPa.
4. A method of producing a ceramic end plate coating according to any of claims 1-3, characterized in that the raw material of the atmospheric plasma spraying contains Al2O3And (3) powder.
5. The method of claim 4, wherein said atmospheric plasma spray feedstock comprises Al2O3Powder and other one or more kinds of powderAl mentioned above2O3The mass ratio of the powder to the other one or more powder is 8: 1-12: 1;
and/or the raw materials for the atmospheric plasma spraying are any one of the following three combinations: ZrO (ZrO)2And Al2O3Powder, AlN and Al2O3Powder of, or of, Si3N4And Al2O3And (3) powder.
6. The method of making a ceramic end plate coating of claim 5, wherein said Al is2O3The mass ratio of the powder to the other powder or the other powders is 9: 1.
7. The method of forming a ceramic end plate coating according to claim 5, wherein said atmospheric plasma spraying is performed from AlN and Al2O3And (3) powder.
8. A method of producing a ceramic coating for a metal end plate according to any one of claims 1-3, characterized in that the metal end plate is further subjected to a sand blasting and a preheating treatment before being subjected to the atmospheric plasma spraying.
9. The method of forming a ceramic coating on a metal end plate of claim 8, wherein said grit blasting is performed on the metal end plate with 10-25 mesh corundum sand at an air pressure of 0.5-1 MPa;
and/or the preheating temperature is 80-200 ℃.
10. The method of forming a ceramic end plate coating according to claim 9, wherein said preheating is at a temperature of 100 ℃.
11. The method of making a ceramic end plate coating according to claim 8, wherein a cleaning process is further performed before said grit blasting and/or after said grit blasting.
12. The method of making a ceramic end plate coating according to claim 11, wherein said cleaning prior to grit blasting is an alcohol cleaning.
13. The method of making a ceramic end plate coating according to claim 11, wherein said post-grit blasting cleaning comprises:
selecting 15-35 g/L NaOH and 20-30 g/L NaCO3Treating the metal end plate for 1-5 min at 20-45 ℃ by using the mixed solution as a degreasing agent; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1-5 min at the temperature of 20-25 ℃;
or treating the metal end plate by using a neutral organic solvent at the temperature of 20-25 ℃ for 1-5 min; selecting 300-400 g/L HNO3The solution is used as a pickling agent and is treated for 1 to 5min at the temperature of 20 to 25 ℃.
14. The method of making a ceramic end plate metal coating of claim 13, wherein said NaOH and NaCO are3The mass ratio of (A) to (B) is 1: 2-1: 5;
and/or the neutral organic solvent is acetone.
15. The method of making a ceramic end plate metal coating of claim 14, wherein said NaOH and NaCO are3The mass ratio of (A) to (B) is 1: 3.
16. The method for preparing a ceramic coating for a metal end plate according to any one of claims 1 to 3, wherein the metal end plate is further subjected to a sealing treatment after the atmospheric plasma spraying.
17. The method of producing a ceramic coating for a metal end plate according to claim 16, wherein the sealing treatment is carried out by mixing the metal end plate with a sealing liquid after the atmospheric plasma spraying.
18. The method of preparing a ceramic coating for a metal end plate according to claim 17, wherein the sealing liquid is a potassium dichromate solution, a nickel acetate solution, a zirconia sol, or an alumina sol.
19. The method for preparing a ceramic coating on a metal end plate according to claim 18, wherein the nickel acetate solution is obtained by mixing acetic acid, nickel acetate and distilled water according to a mass ratio of (1-3): 3-5): 20;
and/or the zirconia sol or the alumina sol is obtained by mixing zirconia or alumina, a solvent, a stabilizer, deionized water and nitric acid, wherein the volume ratio of the solvent to the stabilizer to the deionized water to the nitric acid is 1 (20-50) to 1: 1.
20. The method of making a ceramic end plate coating of metal according to claim 19, wherein said acetic acid, nickel acetate and distilled water are in a mass ratio of 1:5: 20.
21. The method for preparing the metal end plate ceramic coating according to claim 19, wherein the volume ratio of the solvent, the stabilizer, the deionized water and the nitric acid is 1 (25-45): 1: 1.
22. The method of making a ceramic coating for a metal end plate of claim 21, wherein the solvent, stabilizer, deionized water and nitric acid are present in a volume ratio of 1:25:1:1 or 1:45:1: 1.
23. The method of forming a ceramic end plate coating of claim 19, wherein said zirconia or alumina is available from watei chemical trade, shanghai ltd, of tetaiaceae, and wherein said zirconia powder is available under the designation AMPERIT831 and said alumina powder is available under the designation AMPERIT 740.
24. The method of making a ceramic end plate coating according to claim 18,
when the hole sealing liquid is a potassium dichromate solution, the concentration of the potassium dichromate solution is 40-75 g/L, the pH value of the potassium dichromate solution is 5-7, the mixing temperature is 80-95 ℃, and the mixing time is 20-45 min;
when the hole sealing liquid is a nickel acetate solution, the concentration of nickel ions in the nickel acetate solution is 1-3 g/L, and the concentration of acetic acid in the nickel acetate solution is 0.017-0.17 g/L; the pH value of the nickel acetate solution is 5-7, the mixing temperature in the hole sealing treatment is 80-95 ℃, and the mixing time in the hole sealing treatment is 20-45 min;
and when the hole sealing liquid is zirconia sol or alumina sol, immersing the metal end plate into the hole sealing liquid, pulling the metal end plate to obtain the metal end plate coated with the hole sealing liquid on the surface, and carrying out heat treatment on the metal end plate coated with the hole sealing liquid on the surface.
25. The method of making a ceramic end plate metal coating of claim 24, wherein said pulling is at a rate of 0.1 to 0.5 mm/s;
and/or, the heat treatment is carried out in a muffle furnace;
and/or the temperature of the heat treatment is 100-300 ℃;
and/or the time of the heat treatment is 10-30 min;
and/or repeating the steps of immersing, pulling and heat treating for 5-30 times.
26. A ceramic end plate coating produced by the method of producing a ceramic end plate coating according to any one of claims 1 to 25.
27. The metal header ceramic coating of claim 26 wherein said metal header ceramic coating comprises a ceramic layer and a microporous layer, one side of said ceramic layer being adjacent said metal header and the other side of said ceramic layer being adjacent said microporous layer, said ceramic layer having a columnar crystal structure, said ceramic layer and said microporous layer being parallel to one another;
and/or the thickness of the metal end plate ceramic coating is 10-100 mu m, the bonding strength is greater than 100MPa, the porosity is 1-10%, the percentage refers to the percentage of the pore volume in the metal end plate ceramic coating to the total volume of the metal end plate ceramic coating, and the elastic modulus ranges from 50-100 GPa.
28. The ceramic end plate metal coating of claim 27 further comprising a hole sealing layer on the surface of said ceramic end plate metal coating, said hole sealing layer having a thickness of 1 to 20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810552971.5A CN110629150B (en) | 2018-05-31 | 2018-05-31 | Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810552971.5A CN110629150B (en) | 2018-05-31 | 2018-05-31 | Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110629150A CN110629150A (en) | 2019-12-31 |
| CN110629150B true CN110629150B (en) | 2021-07-23 |
Family
ID=68966229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810552971.5A Active CN110629150B (en) | 2018-05-31 | 2018-05-31 | Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110629150B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113549860B (en) * | 2021-06-22 | 2023-03-21 | 河南科技大学 | Composite ceramic coating for motor insulating bearing and preparation method thereof |
| CN116285446A (en) * | 2023-05-15 | 2023-06-23 | 佛山桃园先进制造研究院 | Wear-resistant coating, powder, preparation method, wear-resistant treatment method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254415A (en) * | 1992-04-09 | 1993-10-19 | Saft America Inc. | Stacked cell array bipolar battery with thermal sprayed container and cell seal |
| CN101960660A (en) * | 2008-03-08 | 2011-01-26 | 于利奇研究中心有限公司 | Sealing arrangement for high-temperature fuel cell stack |
| CN102723162A (en) * | 2012-07-09 | 2012-10-10 | 中国科学院电工研究所 | A stainless steel skeleton Nb3Sn superconducting magnet solenoid coil |
| CN102963061A (en) * | 2012-12-03 | 2013-03-13 | 上海理工大学 | Nano columnar crystal thermal barrier coating layer and preparation method thereof |
-
2018
- 2018-05-31 CN CN201810552971.5A patent/CN110629150B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254415A (en) * | 1992-04-09 | 1993-10-19 | Saft America Inc. | Stacked cell array bipolar battery with thermal sprayed container and cell seal |
| CN101960660A (en) * | 2008-03-08 | 2011-01-26 | 于利奇研究中心有限公司 | Sealing arrangement for high-temperature fuel cell stack |
| CN102723162A (en) * | 2012-07-09 | 2012-10-10 | 中国科学院电工研究所 | A stainless steel skeleton Nb3Sn superconducting magnet solenoid coil |
| CN102963061A (en) * | 2012-12-03 | 2013-03-13 | 上海理工大学 | Nano columnar crystal thermal barrier coating layer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110629150A (en) | 2019-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2019422376B2 (en) | Modified austenitic stainless steel having good high-temperature creep resistance performance and preparation method therefor | |
| WO2019172160A1 (en) | Electrolysis electrode and method for manufacturing same | |
| US11908600B2 (en) | Preparation device and method of ceramic coating on a sintered type NdFeB permanent magnet | |
| CN104562128B (en) | A kind of method for preparing thermal protection ceramic layer on metal or metallic composite surface | |
| CN101260556B (en) | A Method of Improving the Fatigue Life of Light Alloy Micro-arc Oxidation Coating | |
| US11530485B2 (en) | Ultralimit alloy and preparation method therefor | |
| CN110629150B (en) | Ceramic coating on surface of metal end plate of fuel cell and preparation method thereof | |
| CN109161890B (en) | A kind of SiO2 micro-arc oxidation composite coating and preparation method thereof | |
| CN108977865B (en) | Preparation method of 5XXX aluminum and aluminum alloy surface high-corrosion-resistance single-compact micro-arc oxidation film layer | |
| CN112756238B (en) | A method for preparing silicon dioxide hydrogen barrier coating on the inner wall of 316L stainless steel pipe | |
| TW574433B (en) | Electrode for gas evolution and method of production | |
| CN110318050A (en) | A kind of aluminium base/anode oxide film composite coating and its preparation method and application | |
| CN104324726A (en) | Preparation and coating method for metal-carrier monolithic catalyst | |
| JP4728306B2 (en) | Electrostatic chuck member and manufacturing method thereof | |
| CN112195491A (en) | SiC-Al based on micro-arc oxidation2O3Method for producing a coating | |
| CN112239880A (en) | Micro-arc oxidation electrolyte for preparing high-corrosion-resistance and wear-resistance coating on surface of magnesium alloy, and preparation method and application thereof | |
| CN110093649B (en) | Aluminum alloy end plate coating, preparation method thereof, end plate containing aluminum alloy end plate coating and fuel cell | |
| CN106929793B (en) | Composite material, method for spraying coating on metal substrate and anticorrosive coating | |
| CN109338367A (en) | A kind of process removing plasma spraying NiAl coating | |
| CN102071388A (en) | Method for preparing anticorrosive coating for magnesium and lithium alloy | |
| JPS62232860A (en) | Gas diffusion electrode and manufacture thereof | |
| CN101435081B (en) | No-voltage chemical membrane preparing and low voltage electrochemical membrane preparing combined process for magnesium alloy surface | |
| CN112103517B (en) | Preparation method of porous nickel-loaded perovskite catalyst | |
| CN115354316A (en) | Ni/Al intermetallic compound coating and preparation method thereof | |
| CN112103519A (en) | Porous nickel-loaded perovskite catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |