CN112144027A - TiN deposited on stainless steel surfacexOyCoated bipolar plate material and preparation method and application thereof - Google Patents
TiN deposited on stainless steel surfacexOyCoated bipolar plate material and preparation method and application thereof Download PDFInfo
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- CN112144027A CN112144027A CN202010794434.9A CN202010794434A CN112144027A CN 112144027 A CN112144027 A CN 112144027A CN 202010794434 A CN202010794434 A CN 202010794434A CN 112144027 A CN112144027 A CN 112144027A
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- stainless steel
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- 239000010935 stainless steel Substances 0.000 title claims abstract description 24
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title abstract 2
- 239000010963 304 stainless steel Substances 0.000 claims abstract description 32
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 13
- 238000007733 ion plating Methods 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 21
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 transition metal nitrides Chemical class 0.000 description 3
- HYZAWROTMYAUAQ-UHFFFAOYSA-N 1-ethyl-3-(6-methylpyridin-2-yl)urea Chemical compound CCNC(=O)NC1=CC=CC(C)=N1 HYZAWROTMYAUAQ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910010421 TiNx Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention is deposition of TiN on the surface of stainless steelxOyA coated bipolar plate material, a preparation method and application thereof. A surface modified 304 stainless steel bipolar plate material is prepared by the following steps: 304 stainless steel is used as a substrate, and a TiNxOy coating is deposited on the surface of the substrate by using a closed field unbalanced magnetron sputtering ion plating technology to obtain the thin film stainless steel bipolar plate with high corrosion resistance. Andthe surface modified 304 stainless steel bipolar plate material is applied to a proton exchange membrane fuel cell bipolar plate. The coating disclosed by the invention is low in production cost, shorter in production period than that of a C coating, and the surface of the coating has ultrahigh hardness and ultrahigh elastic modulus, has better corrosion resistance than that of metal nitride, has good conductivity, and can meet the application standard of U.S. DOE 2025 of a bipolar plate of a proton exchange membrane fuel cell.
Description
Technical Field
The invention relates to a surface modified 304 stainless steel bipolar plate, a preparation method and application thereof, namely TiN is deposited on the surface of 304 stainless steel by a closed field unbalanced magnetron sputtering ion plating technologyxOyThe coating with high corrosion resistance has low production cost, ultrahigh corrosion resistance and good conductivity, and can meet the application standard of the bipolar plate of the proton exchange membrane fuel cell.
Background
The proton exchange membrane fuel cell is a new clean energy device which can directly convert chemical energy into electric energy, and it has the characteristics of no influence of Carnot cycle, high energy conversion rate and less pollution. The bipolar plate is the most significant component of a pem fuel cell and not only accounts for 80% of the total fuel cell weight and nearly the entire volume, but also accounts for 45% of the total fuel cell stack cost. The quality of the bipolar plate is therefore closely related to the efficiency and application of the fuel cell. An excellent bipolar plate should have excellent gas barrier and electrical conductivity, good mechanical properties, excellent corrosion resistance and low cost. Graphite has excellent electrical conductivity and chemical inertness, and thus has been used as a bipolar plate material in the past, but its brittleness, gas permeability and poor machinability make pem fuel cells of great quality and high cost, preventing their further commercial application. While stainless steel has excellent mechanical properties and electrical conductivity, and lower processing costs. However, in the pem fuel cell environment, the stainless steel surface will be corroded to form a passive film, which increases the contact resistance between the gdm and the bipolar plate and affects the working efficiency of the whole cell stack. Therefore, in order to make it useful as a metal bipolar plate, it is highly desirable to develop a conductive coating having high corrosion resistance and meeting practical applications of fuel cells. To improve its corrosion resistance, to reduce its Interfacial Contact Resistance (ICR), and various types of coating materials, such as transition metal nitrides, including ZrN, TiN, and TAN, have been applied to metal surfaces. Although the transition metal nitride coating stainless steel has better corrosion resistance, the high corrosion current density is 10-6～10-5A/cm2The range is still not suitable, and the application to the practical application is difficult. Therefore, a ternary coating bipolar plate which is more durable in the actual battery environment is researched.
Titanium oxynitride (TiN)xOy) Has higher corrosion resistance in acid medium and high potential. It was found in experiments that with TiNxOyWhen the oxygen content in the alloy increases, TiNxOyThe conductivity of the coating can be changed from good to poor, and the corrosion resistance of an acid medium under high potential can be higher and higher. TiN (titanium nitride)xOyThe relationship between the conductivity and the corrosion resistance of the silicon-based alloy and the oxygen content is controlled by a closed-field unbalanced magnetron sputtering ion plating technology, and the content of oxygen plasma is controlled by adjusting the introduction amount of oxygen, so that the silicon-based alloy is an ideal deposition technology. Therefore, the TiNxOy coating prepared by adding a small amount of oxygen atoms into TiN has good conductivity and ultrahigh corrosion resistance, and can meet the application international standard of the bipolar plate of the proton exchange membrane fuel cell.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a surface modified 304 stainless steel bipolar plate material and a preparation method and application thereof, wherein 304 stainless steel is taken as a substrate, the substrate is subjected to grinding and polishing pretreatment, and a TiNxOy coating is deposited on the surface of the substrate by utilizing a closed field unbalanced magnetron sputtering ion plating technology. The corrosion resistance of the metal oxynitride film bipolar plate after the modification treatment is superior to that of the bipolar plate prepared by simply preparing the metal nitride film in the prior art, and the performances of corrosion potential, corrosion current, interface contact resistance and the like meet the requirements of the American DOE 2025 standard.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a surface modified 304 stainless steel bipolar plate material takes 304 stainless steel as a substrate, and TiNxOy coating is deposited on the surface of the substrate by using a closed field unbalanced magnetron sputtering ion plating technology (closed field unbalanced sputtering plating technology) to obtain a thin film stainless steel bipolar plate with high corrosion resistance.
A preparation method of a surface modified 304 stainless steel bipolar plate material comprises the steps of taking 304 stainless steel as a substrate, and depositing a TiNxOy coating on the surface of the substrate by using a closed field unbalanced magnetron sputtering ion plating technology (Teer-650 UDP-4 of British Del), so as to obtain the thin film stainless steel bipolar plate with high corrosion resistance.
Further, the 304 stainless steel substrate is pretreated before surface modification, and the pretreatment method comprises the following steps: cutting a 304 stainless steel bar with the diameter of 30mm into a sample with the diameter of 30mm and the thickness of 3mm by adopting a linear cutting mode, sequentially grinding the sample by using SiC sand paper of 400#, 1000#, 1500# and 2000#, until the surface scratches are consistent, polishing the surface into a mirror surface by using W0.5 diamond abrasive paste, and then performing the following steps of: 1, ultrasonic cleaning for 10min in a mixed solution of alcohol and acetone, then ultrasonic cleaning for 10min in alkaline washing liquid, removing surface oil stains, and improving the success rate of film plating, wherein the ultrasonic frequency is 100Hz, and the ultrasonic cleaning is carried out at room temperature; and after ultrasonic cleaning, washing the surface with deionized water, and drying in a dust-free environment to obtain a pretreated stainless steel sample.
Still further, the TiNxOy coating deposition method comprises the following steps: placing the pretreated stainless steel sample on a sample rack in a cavity of closed-field unbalanced magnetron sputtering ion plating equipment (Teer-650 UDP-4, British Del.), fixing, arranging two Ti targets as sputtering sources in the cavity, closing the door of the cavity, and vacuumizing to 1 × 10-5torr; introducing high-purity argon (99.99%) as protective gas, and starting to operate a coating program: (1) firstly, applying 0.5A current to two Ti targets to prevent the targets from being polluted, cleaning a matrix for 30min, and removing oil stains and oxides on the surface; (2) increasing the current of the Ti target to 6A, depositing for 10-30min, forming a Ti transition layer on the surface of the substrate, and increasing the binding force of the substrate and the coating; (3) introducing high-purity nitrogen (99.99%) and high-purity oxygen (99.99%) as reaction gases, keeping Ti target current at 6A, and passing TiAnd depositing a TiNxOy coating on the surface of the transition layer for 90-140min to obtain the TiNxOy ultra-high corrosion resistance thin-film stainless steel bipolar plate.
Preferably, the Ti target current is 4-8A, more preferably 6A.
Use of a surface-modified 304 stainless steel bipolar plate material as a proton exchange membrane fuel cell bipolar plate.
The invention has the following beneficial effects: the TiNxOy coating deposited by magnetron sputtering is a coating consisting of three elements and has the properties of TiN and TiO 2. The titanium nitride belongs to an interstitial compound, has beautiful golden yellow luster and good chemical stability, the melting point is up to 3000 ℃, and the Vickers microhardness is about 20 GPa. TiO2 has high chemical stability, thermal stability, corrosion resistance and the like. The two are used as films to be jointly deposited on the surface of the stainless steel, so that the surface of the stainless steel is attractive, the density is higher, the crystal defects are fewer, the hardness and the wear resistance are stronger, particularly, the corrosion resistance is greatly improved, and meanwhile, the stainless steel has good conductivity. The TiNxOy film modified 304 stainless steel bipolar plate prepared by the invention is used for carrying out dynamic polarization test on a sample and simulating the starting/closing electrochemical test (by cyclic voltammetry) of a fuel cell automobile (FCV) through an IVIUMSTAT electrochemical workstation, and the test solution is 0.5MH2SO4+4ppmHF (simulating the PEMFCs environment), the interfacial contact resistance was tested after 24h of operation at a stable operating potential (1.2V). The test result shows that the corrosion resistance of the surface modified bipolar plate is greatly improved compared with that of a 316 stainless steel substrate.
Detailed Description
The invention is further described below.
Example 1
A surface modified 304 stainless steel bipolar plate material is prepared by the following steps: cutting a 304 stainless steel bar with the diameter of 30mm into a sample with the diameter of 30mm and the thickness of 3mm by adopting a linear cutting mode, sequentially grinding the sample by using SiC sand paper of 400#, 1000#, 1500# and 2000# until the surface scratches are consistent, polishing the surface into a mirror surface by using W0.5 diamond grinding paste, ultrasonically cleaning the mirror surface in a mixed solution of alcohol and acetone (the volume ratio is 1: 1) for 10min, ultrasonically cleaning the mirror surface in alkaline solution for 10min, removing oil stains on the surface, improving the success rate of film plating, and carrying out the ultrasonic treatment at the ultrasonic frequency of 100Hz at room temperature. And (3) after ultrasonic cleaning, washing the surface with deionized water, and drying in a dust-free environment (preferably in an oven at the temperature of 40-50 ℃) to obtain a pretreated stainless steel sample.
Placing the pretreated stainless steel sample on a sample rack in a cavity of closed-field unbalanced magnetron sputtering ion plating equipment for fixing, arranging two Ti targets as sputtering sources in the cavity, closing a door of the cavity, vacuumizing to 1 × 10-5torr; introducing high-purity argon (more than or equal to 99.99%) as protective gas, and starting to operate a coating program: (1) firstly, applying 0.5A current to two Ti targets to prevent the targets from being polluted, and cleaning a matrix for 30 min; (2) increasing the current of the Ti target to 6A, depositing for 20min, and forming a Ti transition layer on the surface of the substrate; (3) introducing high-purity nitrogen (not less than 99.99%) and high-purity oxygen (not less than 99.99%) as reaction gases, wherein the nitrogen flow is 30sccm, the oxygen flow is 5sccm, the Ti target current is kept at 6A, depositing a TiNxOy coating on the surface of the Ti transition layer, and depositing for 100min to obtain the TiNxOy film.
The corrosion resistance of a sample in a simulated fuel cell environment is tested by an IVIUM electrochemical workstation, a standard three-electrode system is adopted, the sample is taken as a working electrode, a platinum electrode is taken as a counter electrode, a Saturated Calomel Electrode (SCE) is taken as a reference electrode, and a test solution is 0.5MH2SO4+4ppmHF (simulating the PEMFCs environment) and a test temperature of 70 ℃. The sample was first stabilized at Open Circuit Potential (OCP) for 1h and tested for zeta potential polarization (-0.4V)SCE～1.2VSCE) The curves, as well as the corrosion resistance of a simulated Fuel Cell Vehicle (FCV) during 6000 cycles of start-up and shut-down (minimum potential 1.1V, maximum potential 1.6V, sweep rate 500mV/s), and the samples were tested for interfacial contact resistance values.
The results show that the open circuit potential of the TiNxOy film prepared in this example is 0.35V, the corrosion potential is 0.314V, and the corrosion current density is 2.05E-8A cm-2The current density is stabilized at 6.25E at the highest potential of 1.6V after 6000 cycles of simulated start-up and shutdown-5A cm-2The interfacial contact resistance of the coating at 1.4MPa was 9.1 m.OMEGA.cm2。
Example 2
A surface modified 304 stainless steel bipolar plate material is prepared by the following steps: cutting a 304 stainless steel bar with the diameter of 30mm into a sample with the diameter of 30mm and the thickness of 3mm by adopting a linear cutting mode, sequentially grinding the sample by using SiC sand paper of 400#, 1000#, 1500# and 2000# until the surface scratches are consistent, polishing the surface into a mirror surface by using W0.5 diamond grinding paste, ultrasonically cleaning the mirror surface in a mixed solution of alcohol and acetone (the volume ratio is 1: 1) for 10min, ultrasonically cleaning the mirror surface in alkaline solution for 10min, removing oil stains on the surface, improving the success rate of film plating, and carrying out the ultrasonic treatment at the ultrasonic frequency of 100Hz at room temperature. And (3) after ultrasonic cleaning, washing the surface with deionized water, and drying in a dust-free environment (preferably in an oven at the temperature of 40-50 ℃) to obtain a pretreated stainless steel sample.
Placing the pretreated stainless steel sample on a sample rack in a cavity of closed-field unbalanced magnetron sputtering ion plating equipment for fixing, arranging two Ti targets as sputtering sources in the cavity, closing a door of the cavity, vacuumizing to 1 × 10-5torr; introducing high-purity argon (more than or equal to 99.99%) as protective gas, and starting to operate a coating program: (1) firstly, applying 0.5A current to two Ti targets to prevent the targets from being polluted, and cleaning a matrix for 30 min; (2) increasing the current of the Ti target to 6A, depositing for 30min, and forming a Ti transition layer on the surface of the substrate; (3) introducing high-purity nitrogen (not less than 99.99%) and high-purity oxygen (not less than 99.99%) as reaction gases, wherein the flow rate of the nitrogen is 20sccm, the flow rate of the oxygen is 3sccm, the Ti target current is kept at 4A, depositing a TiNxOy coating on the surface of the Ti transition layer, and depositing for 90min to obtain the TiNxOy film.
Example 3
In this example, the Ti target current is kept at 8A, a TiNxOy coating is deposited on the surface of the transition layer of Ti, and the TiNxOy film is obtained after deposition for 140 min.
The other protocol of this example is the same as example 2.
Example 4
Use of the surface modified 304 stainless steel bipolar plate material prepared in examples 1, 2 and 3 above as a proton exchange membrane fuel cell bipolar plate.
Claims (7)
1. A surface modified 304 stainless steel bipolar plate material is characterized in that 304 stainless steel is used as a substrate of the surface modified 304 stainless steel bipolar plate material, and a TiNxOy coating is deposited on the surface of the substrate by using a closed field unbalanced magnetron sputtering ion plating technology, so that a thin film stainless steel bipolar plate with high corrosion resistance is obtained.
2. The method for preparing the surface-modified 304 stainless steel bipolar plate material according to claim 1, wherein the method comprises the following steps: 304 stainless steel is used as a substrate, a TiNxOy coating is deposited on the surface of the substrate by using a closed field unbalanced magnetron sputtering ion plating technology, and the thin film stainless steel bipolar plate with high corrosion resistance is obtained.
3. The method of making a surface modified 304 stainless steel bipolar plate material of claim 2, wherein said 304 stainless steel substrate is pretreated prior to surface modification by: cutting a 304 stainless steel bar with the diameter of 30mm into a sample with the diameter of 30mm and the thickness of 3mm by adopting a linear cutting mode, sequentially grinding the sample by using SiC sand paper of 400#, 1000#, 1500# and 2000#, until the surface scratches are consistent, polishing the surface into a mirror surface by using W0.5 diamond abrasive paste, and then performing the following steps of: 1, ultrasonic cleaning for 10min in a mixed solution of alcohol and acetone, then ultrasonic cleaning for 10min in alkaline washing liquid, removing surface oil stains, and improving the success rate of film plating, wherein the ultrasonic frequency is 100Hz, and the ultrasonic cleaning is carried out at room temperature; and after ultrasonic cleaning, washing the surface with deionized water, and drying in a dust-free environment to obtain a pretreated stainless steel sample.
4. The method of preparing the surface modified 304 stainless steel bipolar plate material of claim 2 or 3, wherein the TiNxOy coating is deposited by: putting the pretreated stainless steel sample into a closed field unbalanced magnetron sputtering ion plating equipment cavityFixing the sample holder, setting two Ti targets as sputtering sources in the cavity, closing the door of the cavity, and vacuumizing to 1 × 10-5torr; introducing high-purity argon as protective gas, and starting to operate a coating program: (1) firstly, applying 0.5A current to two Ti targets to prevent the targets from being polluted, cleaning a matrix for 30min, and removing oil stains and oxides on the surface; (2) increasing the current of the Ti target to 6A, depositing for 10-30min, forming a Ti transition layer on the surface of the substrate, and increasing the binding force of the substrate and the coating; (3) introducing high-purity nitrogen and high-purity oxygen as reaction gases, keeping the current of the Ti target at 6A, and depositing a TiNxOy coating on the surface of the transition layer of Ti for 90-140min to obtain the TiNxOy ultra-high corrosion resistance thin-film stainless steel bipolar plate.
5. The method of making a surface modified 304 stainless steel bipolar plate material of claim 4, wherein said Ti target current is 4-8A.
6. The method of making a surface modified 304 stainless steel bipolar plate material of claim 5, wherein said Ti target current is 6A.
7. The use of the surface modified 304 stainless steel bipolar plate material of claim 1 as a proton exchange membrane fuel cell bipolar plate.
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| CN112803033A (en) * | 2021-02-23 | 2021-05-14 | 北京大学 | Film for fuel cell metal bipolar plate and preparation method thereof |
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2020
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| JIE JIN ET AL.: ""Investigation of incorporating oxygen into TiN coating to resist high potential effects on PEMFC bipolar plates in vehicle applications"" * |
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| CN112803033A (en) * | 2021-02-23 | 2021-05-14 | 北京大学 | Film for fuel cell metal bipolar plate and preparation method thereof |
| CN112803033B (en) * | 2021-02-23 | 2023-10-20 | 北京大学 | Film for fuel cell metal bipolar plate and preparation method thereof |
| CN113328111A (en) * | 2021-05-25 | 2021-08-31 | 上海电力大学 | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof |
| CN113328111B (en) * | 2021-05-25 | 2023-04-21 | 上海电力大学 | Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof |
| CN113506887A (en) * | 2021-06-03 | 2021-10-15 | 浙江工业大学 | Method for preparing TiCxNy coating on surface of stainless steel and application |
| CN113675419A (en) * | 2021-08-20 | 2021-11-19 | 四川大学 | Surface modified titanium bipolar plate, preparation method thereof and application thereof in proton exchange membrane fuel cell |
| CN114214658A (en) * | 2021-12-14 | 2022-03-22 | 中国科学院大连化学物理研究所 | Composite coating for water electrolysis metal bipolar plate and preparation method thereof |
| CN114635115A (en) * | 2022-03-21 | 2022-06-17 | 山东大学 | Antifriction and wear-resistant coating with strong synergistic effect with lubricating oil friction modification additive |
| CN114908318A (en) * | 2022-04-06 | 2022-08-16 | 四川大学 | Method for sputtering multilayer coating on titanium substrate surface through direct current reaction |
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