CN114447356A - Hydrophilic coating and preparation method thereof - Google Patents
Hydrophilic coating and preparation method thereof Download PDFInfo
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- CN114447356A CN114447356A CN202210065851.9A CN202210065851A CN114447356A CN 114447356 A CN114447356 A CN 114447356A CN 202210065851 A CN202210065851 A CN 202210065851A CN 114447356 A CN114447356 A CN 114447356A
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- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000005260 corrosion Methods 0.000 claims abstract description 40
- 230000007797 corrosion Effects 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000788 chromium alloy Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007733 ion plating Methods 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Abstract
The invention provides a hydrophilic coating, which comprises a connecting layer, an anti-corrosion layer and a hydrophilic layer, wherein the connecting layer is distributed on the upper surface of a substrate, the anti-corrosion layer is distributed on the upper surface of the connecting layer, and the hydrophilic layer is distributed on the upper surface of the anti-corrosion layer; the hydrophilic layer is of a porous structure; the material of the hydrophilic layer is any one selected from the group consisting of A, B, C, D, A is a mixture of titanium dioxide and silver oxide, B is a mixture of titanium dioxide and copper oxide, C is a mixture of chromium sesquioxide and niobium pentoxide, and D is a mixture of chromium sesquioxide and silver oxide. According to the hydrophilic coating provided by the invention, the structure of the hydrophilic layer is a porous structure, so that the coating has hydrophilic performance, the corrosion resistance and hydrophilic performance of the bipolar plate are improved, and the service life of a battery is prolonged.
Description
The technical field is as follows:
the invention relates to the technical field of fuel cell bipolar plate surface coatings, in particular to a hydrophilic coating and a preparation method thereof.
Background art:
a hydrogen fuel cell is a power generation device that directly converts chemical energy of hydrogen and oxygen into electrical energy. The basic principle is the reverse reaction of electrolyzed water, hydrogen and oxygen are supplied to the anode and cathode respectively, and after the hydrogen diffuses out through the anode and reacts with the electrolyte, electrons are released to reach the cathode through an external load. High efficiency operation of the fuel cell involves the transport of water away from the cathode to prevent the accumulation and blockage of flow channels for distributing reactants, resulting in cell power decay, as water is produced at the cathode due to oxidation of the hydrogen fuel. Therefore, in order to prevent the flow channel from being blocked by the water generated from the cathode, the surface of the bipolar plate needs to have certain water management characteristics.
Fuel cell bipolar plate materials include metals, graphite, and the like. The metal bipolar plate has excellent electrical conductivity and good mechanical properties, and is applied to most fuel cell bipolar plates. However, the untreated fuel cell bipolar plate can be severely corroded under the influence of the external environment, and the conductivity of the bipolar plate is reduced.
The fuel cell is applied to the fields of spaceflight, automobiles, airplanes and the like, and the performance requirements of different environments on the fuel cell are different, so that a composite coating is urgently needed to be prepared to solve the corrosion resistance and the hydrophilic performance of the bipolar plate of the fuel cell.
The invention content is as follows:
in order to solve the problems, the invention provides a hydrophilic coating and a preparation method thereof.
The technical scheme of the invention is realized as follows: a hydrophilic coating comprising a connecting layer, a corrosion resistant layer and a hydrophilic layer, wherein the connecting layer is distributed on the upper surface of a substrate, the corrosion resistant layer is distributed on the upper surface of the connecting layer, and the hydrophilic layer is distributed on the upper surface of the corrosion resistant layer; the hydrophilic layer is of a porous structure; the material of the hydrophilic layer is any one of the group consisting of A, B, C and D, wherein A is a mixture of titanium dioxide and silver oxide, B is a mixture of titanium dioxide and copper oxide, C is a mixture of chromium oxide and niobium pentoxide, and D is a mixture of chromium oxide and silver oxide.
In some embodiments, further comprising when the material of the hydrophilic layer is the a or the B, the content of titanium is 5 at% to 95 at%; when the hydrophilic layer is made of the C, the content of chromium is 80at percent to 98at percent; when the hydrophilic layer is made of the material D, the content of chromium is 10at percent to 95at percent.
In some embodiments, the proportion of the volume of the porous structure in the hydrophilic layer is 30-80%, and the pore size of the porous structure is 50-500 nm.
In some embodiments, further comprising, the hydrophilic layer has a thickness of 0.5-1 μm.
In some embodiments, further comprising the contact angle of the hydrophilic layer surface is less than 30 °.
In some embodiments, the material of the corrosion-resistant layer is an amorphous titanium alloy doped with at least one element selected from the group consisting of niobium, chromium, tantalum, copper, hafnium, zirconium, vanadium, silicon, boron, iridium, and ruthenium; when the titanium alloy is doped with no more than 4 elements, the titanium content is 90at percent to 99at percent; when the titanium alloy is doped with five or more than five elements, the atomic percentage of each element doped is equal.
In some embodiments, the corrosion-resistant layer has a thickness of 50-100nm, and is subjected to potentiostatic polarization test by using an electrochemical workstation, the test potential is 0.84V, and the corrosion current density is lower than 0.01 mu A/cm2。
In some embodiments, the material of the connection layer is a titanium alloy doped with niobium or molybdenum or a chromium alloy doped with niobium or molybdenum.
In some embodiments, further comprising the connecting layer having a thickness of 20-40 nm.
In addition, the application also provides a preparation method of the hydrophilic coating, which comprises the following steps:
(1) cleaning the base material;
(2) depositing a connecting layer on the upper surface of the substrate by using a magnetron sputtering method, wherein the raw material is an alloy target smelted according to the component proportion of the connecting layer, the current of the alloy target is 5-50A during deposition, the working gas is argon, and the deposition bias is-50V-800V;
(3) depositing an anti-corrosion layer on the connecting layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of the anti-corrosion layer, the current of the alloy target material is 50-300A during deposition, and the working gas is argon;
(4) depositing a hydrophilic layer on the corrosion-resistant layer, wherein the specific process is as follows: depositing a prefabricated layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target smelted according to the component proportion of the hydrophilic layer, the current of the alloy target is 50-150A during deposition, the working gas is argon, and the deposition bias voltage is-50V to-800V; carrying out post-treatment on the prefabricated layer by adopting a micro-arc oxidation method, putting the bipolar plate deposited with the prefabricated layer into electrolyte, wherein the electrolyte is selected from any one of the group consisting of sodium borate, sodium phosphate, sodium carbonate and sodium sulfate, and the prefabricated layer forms a large amount of porous structures due to the release of gas accompanied with the oxidation process in the electrolysis process; in the micro-arc oxidation treatment process, the pulse voltage is 200V-600V, the frequency is 200-600 HZ, the pulse width is 100-500 mus, and the oxidation time is 60-2400 s.
The invention has the beneficial effects that:
(1) the invention provides a hydrophilic coating, which is characterized in that the hydrophilic coating with a porous structure is deposited, so that the contact angle of the surface of the hydrophilic coating is smaller than 30 degrees, the flow channel blockage caused by water generated by a cathode is avoided, and the surface of a bipolar plate has certain water management characteristic and has better conductivity.
(2) The hydrophilic coating prepared by the micro-arc oxidation method has good pore uniformity, can control the size of a contact angle according to parameters such as electrolytic pulse voltage, time and the like, and has higher flexibility.
(3) The material of the corrosion-resistant layer is amorphous titanium alloy, and the titanium alloy has excellent electric conduction and corrosion resistance and mechanical strength, so that the bipolar plate is prevented from being seriously corroded, and the electric conduction and corrosion resistance of the bipolar plate are improved.
Description of the drawings:
FIG. 1 is a schematic view of the structure of a hydrophilic coating according to the present invention.
In the figure: 1, a substrate; 2 a connecting layer; 3, a corrosion resistant layer; 4 a hydrophilic layer.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention more readily understood by those skilled in the art, and thus will more clearly and distinctly define the scope of the invention.
Example 1
Referring to fig. 1, a hydrophilic coating comprises a connecting layer 2, a corrosion-resistant layer 3 and a hydrophilic layer 4, wherein the connecting layer 2 is distributed on the surface of a substrate 1, the corrosion-resistant layer 3 is distributed on the upper surface of the connecting layer 2, and the hydrophilic layer 4 is distributed on the upper surface of the corrosion-resistant layer; the hydrophilic layer is of a porous structure; the material of the hydrophilic layer is a mixture of titanium dioxide and silver oxide.
When the material of the hydrophilic layer 4 is a mixture of titanium dioxide and silver oxide, the content of titanium is 5 at% to 95 at% (e.g., 5 at%, 30 at%, 60 at%, 80 at%, 95 at%).
The volume of the porous structure accounts for 80% of the volume of the hydrophilic layer, and the pore size of the porous structure is 50 nm.
The thickness of the hydrophilic layer 4 is 0.5 μm; the contact angle of the surface of the hydrophilic layer is less than 15 degrees.
The material of the corrosion-resistant layer 3 is an amorphous titanium alloy doped with at least one element selected from the group consisting of niobium, chromium, tantalum, copper, hafnium, zirconium, vanadium, silicon, boron, iridium, and ruthenium, and when the titanium alloy is doped with not more than 4 of the elements, the titanium content is 90 at% to 99 at%. For example, titanium alloy is doped with four elements of chromium, tantalum, copper and hafnium, and the content of titanium is 90 at%; or the titanium alloy is doped with four elements of copper, hafnium, zirconium and vanadium, and the content of titanium is 95 at%; or the titanium alloy is doped with three elements of copper, silicon and iridium, and the content of titanium is 97 at%; or the titanium alloy is doped with two elements of copper and chromium, and the content of titanium is 99 at%; or the titanium alloy is doped with chromium element, and the content of titanium is 99 at%.
When the titanium alloy is doped with five or more than five elements, the atomic percentage of each element doped is equal. For example, the titanium alloy is doped with five elements of niobium, chromium, tantalum, copper and hafnium, wherein the five elements of niobium, chromium, tantalum, copper and hafnium are doped in equal atomic percentage; or the titanium alloy is doped with six elements of copper, vanadium, silicon, boron, iridium and ruthenium, wherein the atomic percentage of each doped element is equal; or the titanium alloy is doped with seven elements of copper, hafnium, zirconium, vanadium, silicon, boron and iridium, wherein the atomic percentage of each doped element is equal. In the present embodiment, "equal" means that the original design is equal, but may include deviations without special meaning or errors that are allowed by those skilled in the art.
The thickness of the corrosion-resistant layer is 100nm, a constant potential polarization test is carried out by adopting an electrochemical workstation, the test potential is 0.84V, and the corrosion current density is lower than 0.01 mu A/cm2(e.g., 0.009 μ A/cm)2、0.007μA/cm2、0.005uA/cm2、0.004uA/cm2Etc.)
The connecting layer is made of titanium alloy or chromium alloy, and both the titanium alloy and the chromium alloy are doped with niobium or molybdenum, such as the titanium alloy is doped with niobium, the titanium alloy is doped with molybdenum, the chromium alloy is doped with niobium, and the chromium alloy is doped with molybdenum.
The thickness of the connecting layer is 20 nm.
Example 2
In this example, unlike example 1, the material of the hydrophilic layer is a mixture of titanium dioxide and copper oxide, and the content of titanium is 5 at% to 95 at% (e.g., 5 at%, 30 at%, 60 at%, 80 at%, 95 at%); the volume of the porous structure accounts for 30% of the volume of the hydrophilic layer, and the pore size of the porous structure is 500 nm; the thickness of the hydrophilic layer is 0.8 mu m, the contact angle of the surface of the hydrophilic layer is 29 degrees, and the thickness of the corrosion-resistant layer is 80 nm; the thickness of the connecting layer is 25 nm.
Example 3
In this example, unlike embodiment 1, the material of the hydrophilic layer is a mixture of chromium sesquioxide and niobium pentoxide, and the content of chromium is 80 at% to 98 at% (e.g., 80 at%, 85 at%, 90 at%, 98 at%); the volume of the porous structure accounts for 60% of the volume of the hydrophilic layer, and the pore size of the porous structure is 200 nm; the thickness of the hydrophilic layer is 0.9 mu m, the contact angle of the surface of the hydrophilic layer is 20 degrees, and the thickness of the corrosion-resistant layer is 60 nm; the thickness of the connecting layer is 30 nm.
Example 4
In this example, unlike embodiment 1, the material of the hydrophilic layer is a mixture of chromium oxide and silver oxide, and the content of chromium is 10 at% to 95 at% (e.g., 10 at%, 30 at%, 60 at%, 80 at%, 95 at%); the volume of the porous structure accounts for 45% of the volume of the hydrophilic layer, and the pore size of the porous structure is 350 nm; the thickness of the hydrophilic layer is 1 micrometer, the contact angle of the surface of the hydrophilic layer is 26 degrees, and the thickness of the corrosion-resistant layer is 50 nm; the thickness of the connecting layer is 40 nm.
Example 5
The application also provides a preparation method of the hydrophilic coating, which is characterized by comprising the following steps: the method comprises the following steps:
(1) cleaning the base material;
(2) and depositing a connecting layer on the upper surface of the substrate by using a magnetron sputtering method, wherein the raw material is an alloy target smelted according to the component proportion of the connecting layer, the current of the alloy target is 5-50A during deposition, the working gas is argon, and the deposition bias is-50V-800V.
(3) And depositing an anti-corrosion layer on the connecting layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target smelted according to the component proportion of the anti-corrosion layer, the current of the alloy target is 50-300A during deposition, and the working gas is argon.
(4) Depositing a hydrophilic layer on the corrosion-resistant layer, wherein the specific process is as follows: depositing a prefabricated layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of a hydrophilic layer, the current of the alloy target material is 50-150A during deposition, the working gas is argon, and the deposition bias voltage is-50V to-800V; carrying out post-treatment on the prefabricated layer by adopting a micro-arc oxidation method, putting the bipolar plate deposited with the prefabricated layer into electrolyte, wherein the electrolyte is selected from any one of the group consisting of sodium borate, sodium phosphate, sodium carbonate and sodium sulfate, and the prefabricated layer forms a large amount of porous structures due to the release of gas accompanied with the oxidation process in the electrolysis process; in the treatment process, the pulse voltage is 200V-600V, the frequency is 200-600 HZ, the pulse width is 100-500 mus, and the oxidation time is 60-2400 s.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A hydrophilic coating characterized by: the corrosion-resistant coating comprises a connecting layer, a corrosion-resistant layer and a hydrophilic layer, wherein the connecting layer is distributed on the upper surface of a substrate, the corrosion-resistant layer is distributed on the upper surface of the connecting layer, and the hydrophilic layer is distributed on the upper surface of the corrosion-resistant layer; the hydrophilic layer is of a porous structure; the material of the hydrophilic layer is any one of the group consisting of A, B, C and D, wherein A is a mixture of titanium dioxide and silver oxide, B is a mixture of titanium dioxide and copper oxide, C is a mixture of chromium oxide and niobium pentoxide, and D is a mixture of chromium oxide and silver oxide.
2. The hydrophilic coating of claim 1, wherein: when the hydrophilic layer is made of the material A or the material B, the content of titanium is 5at percent to 95at percent; when the hydrophilic layer is made of the C, the content of chromium is 80at percent to 98at percent; when the hydrophilic layer is made of the material D, the content of chromium is 10at percent to 95at percent.
3. The hydrophilic coating of claim 1, wherein: the volume of the porous structure accounts for 30-80% of the volume of the hydrophilic layer, and the pore size of the porous structure is 50-500 nm.
4. The hydrophilic coating of claim 1, wherein: the thickness of the hydrophilic layer is 0.5-1 μm.
5. The hydrophilic coating of claim 1, wherein: the contact angle of the upper surface of the hydrophilic layer is less than 30 degrees.
6. The hydrophilic coating of claim 1, wherein: the material of the corrosion-resistant layer is amorphous titanium alloy, and the titanium alloy is doped with at least one element selected from the group consisting of niobium, chromium, tantalum, copper, hafnium, zirconium, vanadium, silicon, boron, iridium and ruthenium; when the titanium alloy is doped with no more than 4 elements, the titanium content is 90at percent to 99at percent; when the titanium alloy is doped with five or more than five elements, the atomic percentage of each element doped is equal.
7. The hydrophilic coating of claim 1, wherein: the thickness of the corrosion-resistant layer is 50-100nm, a constant potential polarization test is carried out by adopting an electrochemical workstation, the test potential is 0.84V, and the corrosion current density is lower than 0.01 mu A/cm2。
8. The hydrophilic coating of claim 1, wherein: the connecting layer is made of titanium alloy or chromium alloy, the titanium alloy is doped with niobium element or molybdenum element, and the chromium alloy is doped with niobium element or molybdenum element.
9. The hydrophilic coating of claim 1, wherein: the thickness of the connecting layer is 20-40 nm.
10. A preparation method of a hydrophilic coating is characterized by comprising the following steps: the method comprises the following steps:
(1) cleaning the base material;
(2) depositing a connecting layer on the upper surface of the substrate by using a magnetron sputtering method, wherein the raw material is an alloy target smelted according to the component proportion of the connecting layer, the current of the alloy target is 5-50A during deposition, the working gas is argon, and the deposition bias is-50V-800V;
(3) depositing an anti-corrosion layer on the connecting layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of the anti-corrosion layer, the current of the alloy target material is 50-300A during deposition, and the working gas is argon;
(4) depositing a hydrophilic layer on the corrosion-resistant layer, wherein the specific process is as follows: depositing a prefabricated layer by using a cathode filtration arc ion plating method, wherein the raw material is an alloy target smelted according to the component proportion of the hydrophilic layer, the current of the alloy target is 50-150A during deposition, the working gas is argon, and the deposition bias voltage is-50V to-800V; and then, carrying out post-treatment on the prefabricated layer by adopting a micro-arc oxidation method, and putting the bipolar plate deposited with the prefabricated layer into an electrolyte, wherein the electrolyte is selected from any one of the group consisting of sodium borate, sodium phosphate, sodium carbonate and sodium sulfate, and in the micro-arc oxidation method treatment process, the pulse voltage is 200-600V, the frequency is 200-600 HZ, the pulse width is 100-500 mu s, and the oxidation time is 60-2400 s.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116682986A (en) * | 2023-08-02 | 2023-09-01 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009385A (en) * | 2006-01-27 | 2007-08-01 | 通用汽车环球科技运作公司 | Super-hydrophilic nanoporous electrically conductive coatings for PEM fuel cells |
| CN101057350A (en) * | 2004-11-12 | 2007-10-17 | 通用汽车公司 | Hydrophilic surface modification of bipolar plate |
| JP2019057449A (en) * | 2017-09-22 | 2019-04-11 | トヨタ自動車株式会社 | Separator for non-aqueous electrolytic solution secondary battery |
| CN112993298A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Double-functional coating of fuel cell metal bipolar plate |
| CN113903939A (en) * | 2021-09-27 | 2022-01-07 | 中汽创智科技有限公司 | Proton exchange membrane and preparation method thereof |
-
2022
- 2022-01-20 CN CN202210065851.9A patent/CN114447356B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057350A (en) * | 2004-11-12 | 2007-10-17 | 通用汽车公司 | Hydrophilic surface modification of bipolar plate |
| CN101009385A (en) * | 2006-01-27 | 2007-08-01 | 通用汽车环球科技运作公司 | Super-hydrophilic nanoporous electrically conductive coatings for PEM fuel cells |
| JP2019057449A (en) * | 2017-09-22 | 2019-04-11 | トヨタ自動車株式会社 | Separator for non-aqueous electrolytic solution secondary battery |
| CN112993298A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Double-functional coating of fuel cell metal bipolar plate |
| CN113903939A (en) * | 2021-09-27 | 2022-01-07 | 中汽创智科技有限公司 | Proton exchange membrane and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116682986A (en) * | 2023-08-02 | 2023-09-01 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
| CN116682986B (en) * | 2023-08-02 | 2023-12-08 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
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