CN114447356B - Hydrophilic coating and preparation method thereof - Google Patents
Hydrophilic coating and preparation method thereof Download PDFInfo
- Publication number
- CN114447356B CN114447356B CN202210065851.9A CN202210065851A CN114447356B CN 114447356 B CN114447356 B CN 114447356B CN 202210065851 A CN202210065851 A CN 202210065851A CN 114447356 B CN114447356 B CN 114447356B
- Authority
- CN
- China
- Prior art keywords
- layer
- hydrophilic
- corrosion
- doped
- chromium
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 6
- 238000005260 corrosion Methods 0.000 claims abstract description 38
- 230000007797 corrosion Effects 0.000 claims abstract description 38
- 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 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 28
- 239000000463 material Substances 0.000 claims description 18
- 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
- 239000000446 fuel Substances 0.000 claims description 11
- 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
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium 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
- 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
- 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
- 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron 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
- 230000010287 polarization Effects 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000013077 target material Substances 0.000 description 12
- 230000008021 deposition Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000007733 ion plating Methods 0.000 description 4
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 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
- 238000005516 engineering process Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 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
Classifications
-
- 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, 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 hydrophilic layer is made of any one selected from the group consisting of A, B, C, 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. The hydrophilic coating provided by the invention has a porous structure, so that the coating has hydrophilic performance, the corrosion resistance and the hydrophilic performance of the bipolar plate are improved, and the service life of the battery is prolonged.
Description
Technical field:
the invention relates to the technical field of surface coatings of bipolar plates of fuel cells, in particular to a hydrophilic coating and a preparation method thereof.
The background technology is as follows:
a hydrogen fuel cell is a power generation device that directly converts chemical energy of hydrogen and oxygen into electric energy. The basic principle is that the reverse reaction of electrolyzed water supplies hydrogen and oxygen to the anode and the cathode respectively, and after hydrogen diffuses outwards through the anode and reacts with electrolyte, electrons are released and reach the cathode through an external load. The efficient operation of fuel cells involves the transport of water out of the cathode to prevent accumulation and clogging of flow channels for distributing reactants, resulting in a decay in cell power, due to the oxidation of hydrogen fuel to generate water at the cathode. Therefore, in order to avoid the blockage of the flow channels caused by the water generated by the cathode, the bipolar plate surface needs to have certain water management characteristics.
The fuel cell bipolar plate material includes metal, graphite, and the like. The metal bipolar plate has excellent conductivity and good mechanical properties, and is applied to most fuel cell bipolar plates. However, untreated fuel cell bipolar plates undergo severe corrosion under the influence of the external environment, resulting in a decrease in the conductivity of the bipolar plates.
The fuel cell is applied to the fields of aerospace, automobiles, airplanes and the like, and the performance requirements of different environments on the fuel cell are different, so that a composite coating is prepared to solve the corrosion resistance and the hydrophilic performance of a bipolar plate of the fuel cell.
The invention comprises the following steps:
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: the hydrophilic 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 hydrophilic layer is made of any one selected from 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, the hydrophilic layer is made of a material of the A or the B, and the titanium content is 5at% to 95at%; when the hydrophilic layer is made of the material C, the content of chromium is 80at% -98 at%; when the hydrophilic layer is made of the material D, the content of chromium is 10at percent to 95at percent.
In some embodiments, further comprising, the porous structure volume is 30% -80% of the hydrophilic layer volume, and the pore size of the porous structure is 50-500nm.
In some embodiments, further comprising, the hydrophilic layer has a thickness of 0.5-1 μm.
In some embodiments, further comprising, the hydrophilic layer surface has a contact angle of less than 30 °.
In some embodiments, the material of the corrosion-resistant layer is 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 not more than 4 kinds of the elements, the titanium content is 90at% to 99at%; when the titanium alloy is doped with five or more elements, the atomic percentage of each doped element is equal.
In some embodiments, the corrosion-resistant layer has a thickness of 50-100nm, and is subjected to potentiostatic polarization test with an electrochemical workstation at a test potential of 0.84V and a corrosion current density of less than 0.01 μA/cm 2 。
In some embodiments, the material of the connection layer is titanium alloy doped with niobium or molybdenum, or chromium alloy doped with niobium or molybdenum.
In some embodiments, the connection layer further comprises a thickness of 20-40nm.
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 material smelted according to the component proportion of the connecting layer, the current of the alloy target material is 5-50A, the working gas is argon, and the deposition bias voltage is-50V to-800V;
(3) Depositing a corrosion-resistant layer on the connecting layer by using a cathodic filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of the corrosion-resistant 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: firstly, depositing a prefabricated layer by using a cathodic filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of the 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, and placing the bipolar plate deposited with the prefabricated layer into electrolyte, wherein the electrolyte is selected from any one of sodium borate, sodium phosphate, sodium carbonate and sodium sulfate, and the prefabricated layer forms a large number of porous structures due to the release of gas in the oxidation process in the electrolysis process; in the micro-arc oxidation 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.
The beneficial effects of the invention are as follows:
(1) The invention provides a hydrophilic coating, by depositing the hydrophilic coating with a porous structure, 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 better conductivity.
(2) The hydrophilic coating prepared by the micro-arc oxidation method has good pore uniformity, can control the contact angle according to parameters such as electrolysis 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 severely corroded, and the electric conduction and corrosion resistance of the bipolar plate are improved.
Description of the drawings:
FIG. 1 is a schematic illustration of the structure of a hydrophilic coating according to the present invention.
In the figure: 1, a matrix; 2 a connecting layer; 3, a corrosion-resistant layer; 4 hydrophilic layer.
The specific embodiment is as follows:
the preferred embodiments of the present invention will be described in detail below with reference to the attached drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present 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 hydrophilic layer is made of 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 5at% -95 at% (e.g. 5at%, 30at%, 60at%, 80at%, 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 50nm.
The thickness of the hydrophilic layer 4 is 0.5 μm; the contact angle of the hydrophilic layer surface is less than 15 degrees.
The material of the corrosion-resistant layer 3 is amorphous titanium alloy, at least one element selected from the group consisting of niobium, chromium, tantalum, copper, hafnium, zirconium, vanadium, silicon, boron, iridium and ruthenium is doped in the titanium alloy, and when the titanium alloy is doped with no more than 4 elements, the titanium content is 90at% to 99at%. For example, titanium alloy is doped with four elements of chromium, tantalum, copper and hafnium, and the titanium content is 90at%; or titanium alloy doped with four elements of copper, hafnium, zirconium and vanadium, wherein the titanium content is 95at%; or three elements of copper, silicon and iridium are doped in the titanium alloy, and the titanium content is 97at%; or the titanium alloy is doped with copper and chromium, and the titanium content is 99at%; or the titanium alloy is doped with chromium element, and the titanium content is 99at percent.
When the titanium alloy is doped with five or more elements, the atomic percentage of each doped element is equal. For example, five elements of niobium, chromium, tantalum, copper and hafnium are doped in the titanium alloy, wherein the atomic percentages of the five elements of niobium, chromium, tantalum, copper and hafnium are equal; or six elements of copper, vanadium, silicon, boron, iridium and ruthenium are doped in the titanium alloy, 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 this embodiment, "equal" means that the original design purpose is equal, but may include deviations without special meaning or errors allowed by those skilled in the art.
The thickness of the corrosion-resistant layer is 100nm, and an electrochemical workstation is adopted for carrying out constant potential poleChemical test, the test potential is 0.84V, and the corrosion current density is lower than 0.01 mu A/cm 2 (e.g., 0.009. Mu.A/cm) 2 、0.007μA/cm 2 、0.005uA/cm 2 、0.004uA/cm 2 Etc
The material of the connecting layer is titanium alloy or chromium alloy, and the titanium alloy or the chromium alloy is doped with niobium element or molybdenum element, for example, the titanium alloy is doped with niobium element, the titanium alloy is doped with molybdenum element, the chromium alloy is doped with niobium element, and the chromium alloy is doped with molybdenum element.
The thickness of the connecting layer is 20nm.
Example 2
In this example, unlike in example 1, the hydrophilic layer is made of a mixture of titanium dioxide and copper oxide, and the titanium content is 5at% to 95at% (e.g., 5at%, 30at%, 60at%, 80at%, 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 500nm; the thickness of the hydrophilic layer is 0.8 mu m, the contact angle of the surface of the hydrophilic layer is 29 DEG, and the thickness of the corrosion-resistant layer is 80nm; the thickness of the connection layer is 25nm.
Example 3
In this example, unlike example 1, the hydrophilic layer is made of a mixture of chromium oxide and niobium pentoxide, and the content of chromium is 80at% to 98at% (e.g., 80at%, 85at%, 90at%, 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 200nm; the thickness of the hydrophilic layer is 0.9 mu m, the contact angle of the surface of the hydrophilic layer is 20 DEG, and the thickness of the corrosion-resistant layer is 60nm; the thickness of the connecting layer is 30nm.
Example 4
In this example, unlike example 1, the hydrophilic layer is made of a mixture of chromium oxide and silver oxide, and the content of chromium is 10at% to 95at% (such as 10at%, 30at%, 60at%, 80at%, 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 350nm; the thickness of the hydrophilic layer is 1 mu m, the contact angle of the surface of the hydrophilic layer is 26 DEG, and the thickness of the corrosion-resistant layer is 50nm; the thickness of the connecting layer is 40nm.
Example 5
The application also provides a preparation method of the hydrophilic coating, which is characterized in that: 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 material smelted according to the component proportion of the connecting layer, the current of the alloy target material is 5-50A, the working gas is argon, and the deposition bias voltage is-50V to-800V.
(3) And depositing a corrosion-resistant layer on the connecting layer by using a cathodic filtration arc ion plating method, wherein the raw material is an alloy target material smelted according to the component proportion of the corrosion-resistant 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: firstly, depositing a prefabricated layer by using a cathodic 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, and placing the bipolar plate deposited with the prefabricated layer into electrolyte, wherein the electrolyte is selected from any one of sodium borate, sodium phosphate, sodium carbonate and sodium sulfate, and the prefabricated layer forms a large number of porous structures due to the release of gas in 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 mu s, and the oxidation time is 60s-2400s.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. A hydrophilic coating for a bipolar plate of a fuel cell, 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, and the contact angle of the upper surface of the hydrophilic layer is smaller than 30 degrees; the hydrophilic layer is made of any one selected from 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 titanium content is 5at% -95 at%; when the hydrophilic layer is made of the material C, the content of chromium is 80at% -98 at%; 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 50-500nm.
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 material of the corrosion-resistant layer is amorphous titanium alloy, and at least one element selected from the group consisting of niobium, chromium, tantalum, copper, hafnium, zirconium, vanadium, silicon, boron, iridium and ruthenium is doped in the titanium alloy; when the titanium alloy is doped with not more than 4 kinds of the elements, the titanium content is 90at% to 99at%; when the titanium alloy is doped with five or more elements, the atomic percentage of each doped element is equal.
6. The hydrophilic coating of claim 1, wherein: the thickness of the corrosion-resistant layer is 50-100nm, and the electrochemical workstation is adopted to carry out constant potential polarization test, the test potential is 0.84V, and the corrosion current density is lower than 0.01 mu A/cm 2 。
7. The hydrophilic coating of claim 1, wherein: the material of the connecting layer is 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.
8. The hydrophilic coating of claim 1, wherein: the thickness of the connecting layer is 20-40nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210065851.9A CN114447356B (en) | 2022-01-20 | 2022-01-20 | Hydrophilic coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210065851.9A CN114447356B (en) | 2022-01-20 | 2022-01-20 | Hydrophilic coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114447356A CN114447356A (en) | 2022-05-06 |
| CN114447356B true CN114447356B (en) | 2024-04-02 |
Family
ID=81367470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210065851.9A Active CN114447356B (en) | 2022-01-20 | 2022-01-20 | Hydrophilic coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114447356B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114447356A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7482083B2 (en) | Corrosion resistant coated fuel cell bipolar plate with filled-in fine scale porosities | |
| US6864007B1 (en) | Corrosion resistant coated fuel cell plate with graphite protective barrier and method of making the same | |
| EP2817430B1 (en) | Coating with conductive and corrosion resistance characteristics | |
| EP2823079B1 (en) | Corrosion resistant and electrically conductive surface of metal | |
| TWI602344B (en) | Metal plate for separator of solid polymer fuel cell and metal plate for manufacturing the same | |
| TWI610490B (en) | Metal plate for partition of solid polymer fuel cell | |
| CN114447356B (en) | Hydrophilic coating and preparation method thereof | |
| US11133512B2 (en) | Bipolar plate | |
| KR102126183B1 (en) | Diffusion layer and oxygen electrode composite layers of polymer electrolyte membrane water electrolysis apparatus and method for preparing the same and polymer electrolyte membrane water electrolysis apparatus using the same | |
| CN114231925A (en) | Fuel cell metal bipolar plate composite coating and preparation method thereof | |
| CN110970626B (en) | Fuel cell bipolar plate and coating thereof | |
| CN112195482A (en) | Composite titanium anode plate and preparation method thereof | |
| US20240047703A1 (en) | Layer and layer system and electrically conductive plate and electrochemical cell | |
| JP6939747B2 (en) | Electrode plate | |
| CN117468031A (en) | High-conductivity PEM (proton exchange membrane) electrolytic cell diffusion layer and preparation method thereof | |
| JP2019186121A (en) | Bipolar plate |
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 |