CN113549873A - Double-layer coating of fuel cell metal connector - Google Patents
Double-layer coating of fuel cell metal connector Download PDFInfo
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- CN113549873A CN113549873A CN202110692108.1A CN202110692108A CN113549873A CN 113549873 A CN113549873 A CN 113549873A CN 202110692108 A CN202110692108 A CN 202110692108A CN 113549873 A CN113549873 A CN 113549873A
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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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
- C23C14/22—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
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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
Abstract
The invention belongs to the technical field of fuel cell materials. Aiming at the problem of volatilization of Cr of an alloy connector of a solid oxide fuel cell and the problem of easy corrosion of a metal bipolar plate of a proton exchange membrane fuel cell, the invention provides a double-layer coating of a metal connector, wherein the inner layer of the coating is a TiC coating, and the outer layer of the coating is Ti3SiC2Ceramic or doped modified solid solution material (Ti, M)3SiC2Wherein M is selected from one of Nb, Ta, W and V materials. The double-layer coating is characterized in that,has uniform, compact and high adhesive force, can effectively inhibit the outward migration of Cr element contained in a metal connector for a long time, solves the problem of cathode poisoning, and can reduce Cr2O3The growth rate of the membrane reduces the working resistance of the connector and improves the comprehensive working performance of the stainless steel connector; meanwhile, the metal bipolar plate can be used for a metal bipolar plate of a proton exchange membrane fuel cell, and the corrosion resistance and the conductivity of the bipolar plate of the proton exchange membrane fuel cell are effectively improved.
Description
Technical Field
The invention belongs to the technical field of fuel cell materials, and particularly relates to a metal connector coating of a fuel cell.
Background
The Solid Oxide Fuel Cell (SOFC) has the advantages of capability of using carbon-containing Fuel, high power generation efficiency, low power generation cost and the like, and has wide application prospects in the fields of distributed power stations, power sources and the like. Although there are some stacks that have been demonstrated to operate worldwide, their large-scale commercial application is still limited by the materials of the various components. Wherein the connector material is one of the development bottlenecks of the SOFC. The connector (also called connecting plate or bipolar plate) is a key component for assembling the flat SOFC stack, and on one hand, the connector is electrically connected with adjacent monocells; on the other hand, the fuel gas of the anode is separated from the air of the cathode, and the performance of the fuel gas directly influences the output power and the service life of the SOFC electric stack.
After 90 years, with the development of electrolyte materials, the service temperature of solid oxide fuel cells is reduced to 600-800 ℃, so that the alloy can be used as a connector material, wherein the alloy mainly comprises chromium-based alloy, nickel-based alloy and iron-based alloy, and at present, the iron-based alloy represented by SUS430 and Crofer22APU is a main choice of the connector material due to the advantages of low price, good oxidation resistance and electrical conductivity, good matching property of thermal expansion coefficient with other components and the like. Alloy interconnect materials have their own advantages but also have fatal disadvantages, the most fatal of which is the problem of volatilization of chromium compounds. In order to make the connector material have certain oxidation resistance and conductivity under the working environment, the alloy connector material contains certain chromium to generate a chromium oxide film. The chromium oxide forms volatile chromium compounds in the working environment, and the compounds poison the cathode, so that the output performance of the battery is reduced, and finally the aging of the galvanic pile is accelerated.
Aiming at the problem of volatilization of Cr of an alloy connector, a protective coating is applied to the surface of the alloy connectorAn important means. The protective coating applied to the surface of the alloy connector at present mainly comprises: reactive oxide coatings (such as Y, La, Ce and oxides thereof), conductive perovskite coatings and conductive spinel structure coatings. The reaction oxide coating is formed by depositing a thin layer of reaction substances such as Y, La, Ce and the like on the alloy connector, so that the thickness of the film is effectively reduced, and the binding force of the oxide film is increased. However, the use of a large amount of rare earth elements makes the coating expensive, which is not favorable for reducing the cost of the interconnect. The perovskite coating is limited by a preparation method, the film layer is difficult to reach 100% compactness, and oxygen can be diffused through the film layer to continuously increase the thickness of the oxide layer of the substrate; further, the film layer contains a small amount of ion conductivity, and the diffusion of Cr cannot be suppressed completely and effectively. Neither reactive oxide coatings nor perovskite coatings have been commercially applied. Conductive spinel structure coating with molecular formula AB2O4The A and B sites are transition elements, so that the Cr element diffusion resistance is good, and the method is a current research hotspot. However, the stability of the alloy matrix and the coating structure needs to be improved, and the mutual diffusion of the system is easy to occur, so that the components of the oxide layer can be correspondingly changed along with the extension of the working time, the resistance of the connecting plate is increased, and the binding force of the protective film is influenced.
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of low operating temperature, zero emission, high specific power, high energy conversion rate and the like, and have wide prospects in the fields of automotive power supplies, portable equipment, aviation and the like. PEMFCs are mainly composed of a membrane electrode assembly, a bipolar plate, an end plate, a sealing member, and the like. The bipolar plate is a core multifunctional component of the PEMFCs, plays roles in uniformly distributing gas, draining water, conducting heat, conducting electricity and the like, accounts for 60% of the whole fuel cell by mass, accounts for 15% -20% of the cost, and directly influences the service life and the commercialization process of the cell by the performance and the cost. The traditional graphite bipolar plate is gradually replaced by a metal bipolar plate with strong machinability, excellent electric and thermal conductivity and good mechanical property due to large volume, high manufacturing cost and poor mechanical property. However, in the acidic working environment of the battery, the metal polar plate is easy to corrode, the ion transmission efficiency of the proton exchange membrane is reduced due to metal ions formed in the corrosion process, and meanwhile, the interface contact resistance is increased due to a passive film formed on the surface of the metal bipolar plate, so that the performance of the fuel battery is reduced. Based on the characteristics, the novel double-layer coating designed and researched by the invention has the characteristics of compactness, high adhesive force and uniformity, and is a good anti-oxidation corrosion coating for the metal material.
Disclosure of Invention
Aiming at the problem of volatilization of Cr of an alloy connector of a solid oxide fuel cell and the problem of easy corrosion of a metal bipolar plate of a proton exchange membrane fuel cell, the invention provides a double-layer coating of a metal connector, wherein the outer layer is Ti3SiC2Ceramics or their doped modified solid solution materials (Ti, M)3SiC2(M is one of Nb, Ta, W and V), the inner layer is a TiC layer, the double-layer coating has the advantages of uniformity, compactness and high adhesive force, can effectively inhibit the outward migration of Cr element contained in the metal connector for a long time, solves the problem of cathode poisoning, and can reduce Cr2O3The growth rate of the membrane reduces the working resistance of the connector and improves the comprehensive working performance of the stainless steel connector; meanwhile, the metal bipolar plate can be used for a metal bipolar plate of a proton exchange membrane fuel cell, and the corrosion resistance and the conductivity of the bipolar plate of the proton exchange membrane fuel cell are effectively improved.
The invention is realized by the following technical scheme:
a double-layer coating of a metal connector of a fuel cell is provided, wherein the outer layer of the coating is Ti3SiC2Ceramics or their doped modified solid solution materials (Ti, M)3SiC2Wherein M is selected from any one of Nb, Ta, W and V materials, and the inner layer is a TiC layer. The surface of the coating can be oxidized in the use temperature range of the solid oxide fuel cell or in the use environment of the proton exchange membrane fuel cell to form an oxide film with compact microstructure and long-acting effect.
Further, the deposition method of the metal connector coating on the surface of the metal connector comprises the following steps: pretreating the metal connector, and then adding TiC and Ti respectively3SiC2Ceramics or doped modified solid solutions (Ti, M)3SiC2As target material, magnetic control is adoptedTiC and Ti by sputtering or arc ion plating3SiC2Ceramics or doped modified solid solutions (Ti, M)3SiC2The target material is deposited on the surface of the metal connector.
Further, the metal connector is a ferritic stainless steel: any one of SUS430, Crofer22APU, Fe-10Cr, 1.4724, Fe-17Cr-0.2Y, 1.4016, Ferrotherm (1.4742), Fe-18Cr-9W, Fe-20Cr-7W, Fe-20Cr, AL 453, 1.4763(446), FeCrMn (LaTi), Fe-Cr-Mn, Fe-25Cr-DIN 50049, Fe-25Cr-0.1Y-2.5Ti, Fe-25Cr-0.2Y-1.6Mn, Fe-25Cr-0.4La, Fe-25Cr-0.3Zr, Fe26CrTiY, Fe26CrTiNbY, Fe26CrMoTiY, E-Brite, Al29-4C or Fe-30 Cr.
Further, said Ti3SiC2Ceramics or doped modified solid solutions (Ti, M)3SiC2The preparation method comprises the following steps: selecting original powder materials comprising Ti powder, silicon powder and graphite powder, wherein the solid solution also comprises any one of Nb powder, Ta powder, W powder and V powder, wet-mixing the powder on a ball mill for 24 hours by a wet-mixing method, taking out the powder, naturally drying the powder in the air, and sieving the powder for later use; and sintering the sample in a hot pressing furnace by adopting a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 1000-1700 ℃, the temperature is kept for 15-60 minutes, the hot pressing pressure is 10-60 MPa, and flowing argon is used as protective gas.
Further, the preparation method of the self-made TiC target material comprises the following steps: the original powder materials are Ti powder and graphite powder, wet mixing is carried out on a ball mill for 12 hours by adopting a wet mixing method, then the materials are taken out for natural air drying, and then sieving is carried out for standby; the material is prepared by sintering in a hot pressing furnace by adopting a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 900-1300 ℃, the temperature is kept for 20-60 minutes, the hot pressing pressure is 10-30 MPa, and flowing argon is used as protective gas.
Further, an arc ion plating device or a magnetron sputtering device is utilized to deposit a coating on the surface of the alloy, the sample is hung on a sample rack of the equipment during the deposition of the coating, the stand column for hanging the sample can rotate, the rotating stand column can revolve along with the rotating table, and the rotation of the sample is to obtain uniform coating.
Furthermore, when a metal connector sample is prepared, the sample is pretreated, firstly, sand paper is selected to polish the metal connector, namely, 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# metallographic sand paper is used for polishing step by step, then the polished metal connector sample is subjected to ultrasonic cleaning for 5-30 min respectively through acetone, alcohol and deionized water, and then the sample is dried in the air for later use.
Further, the arc ion plating method is characterized in that before the coating is prepared, the vacuum chamber is pre-vacuumized until the back bottom vacuum is 5 multiplied by 10-3And after Pa, applying 500V negative pulse bias voltage on the substrate to carry out back-splash cleaning on the substrate for 5-15 min, and removing pollutants and an oxidation layer on the surface of the substrate. Then opening the Ar flow valve, wherein the Ar gas flow is 50ml/min, and controlling the working air pressure in the vacuum chamber by adjusting the pumping speed of the molecular pump to maintain the working air pressure at 0.30-0.40Pa and the heating temperature of the chamber at 300-500 ℃. Firstly, a TiC coating is deposited, namely a direct-current power supply is turned on, the arc current is 50-80A, the bias voltage is-300-400V, and the sputtering time is 10-30 min. Then depositing an outer layer of Ti3SiC2Or doping modified solid solution material (Ti, M)3SiC2(M ═ Nb, Ta, V or W), adjusting the temperature of the chamber to 200-700 ℃, preserving the temperature for 15min, then turning on a direct current power supply, wherein the arc current is 30-70A, the bias voltage is-400-500V, and the sputtering time is 10-60 min. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped.
The magnetron sputtering method is characterized in that before the coating is prepared, the coating is firstly pre-vacuumized to 5 multiplied by 10-4Pa to minimize contamination of residual gases during sputtering. And introducing high-purity Ar gas with the flow rate of 30ml/min after the vacuum degree required by the experiment is reached, and adjusting the working air pressure to be kept at 0.25-0.35 Pa. First using Ar before the start of deposition+And cleaning the target to remove pollutants on the surface of the target, wherein the cleaning time is 5-15 min. And then heating the sample to 100-800 ℃, and preserving heat for 15min to ensure that the temperature of the whole sample is uniform and then starting sputtering to prepare the coating. In the coating preparation process, firstly, the TiC inner layer is prepared, the sputtering power is 0.1-2.5 kw, and the sputtering time is 1-2 h. Then sputtering an outer Ti layer3SiC2Or doping modified solid solution material (Ti, M)3SiC2(M ═ Nb, Ta, V or W), sputtering power of 0.1 to 2.5kw, sputtering time of 1 to E-And 6 h. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped.
A metal interconnect for a fuel cell, the metal interconnect having the coating described above.
The invention relates to a fuel cell metal connector with a novel coating and a preparation method thereof, wherein the outer layer of the novel coating is Ti3SiC2Ceramics and doped modified solid solution material ((Ti, M)3SiC2M is one of Nb, Ta, W and V), and the inner layer is a TiC layer; the preparation method of the metal connector comprises the following steps: pretreating the metal connector; then adopting magnetron sputtering method or arc ion plating method, firstly depositing an inner TiC layer on the surface, and then depositing Ti3SiC2Ceramic or doped modified solid solution layer thereof ((Ti, M)3SiC2And M is one of Nb, Ta, W and V) to obtain a metal connector with a novel double-layer coating attached to the surface. The invention has the beneficial effects that: can obtain a novel uniform, compact and high-adhesion coating which can effectively inhibit the outward migration of Cr element contained in a metal connector and reduce Cr2O3The growth rate of the membrane reduces the working resistance of the connector and improves the comprehensive working performance of the stainless steel connector. Meanwhile, the novel double-layer coating designed and researched by the invention is a good oxidation and corrosion resistant coating for the metal material on the metal connector. In addition, the method has the advantages of simple process, low cost and easy realization of industrial production.
Compared with the prior art, the invention has the following advantages:
1. compared with a reaction oxide coating, the novel coating can easily obtain a coating with expected thickness, the bonding strength of the coating and a substrate is high, the raw materials (Ti, Si and C powder) used by the coating are low in price, and Nb, Ta, W and V powder is expensive but used for doping, is less in use and is easy to industrially popularize.
2. Compared with the perovskite coating, the coating can be dense, outward migration of Cr is effectively blocked, and the coating plays a great and substantial role in protecting the cathode.
3. Compared with the conductive spinel structure coating, the coating has stronger compatibility with an alloy matrix and can keep the stability of the structure for a long time.
4. And direct use of Ti3SiC2Compared with the connector, the connector is easier to process and has better applicability. Ti3SiC2The finished product rate of the connecting body is low, the processing and manufacturing cost is high, certain difficulty exists in synthesizing block materials or components with large size or complex shape, and Ti is limited3SiC2And large-scale application of solid solution materials thereof.
The fuel cell metal connector provided by the invention has uniform and compact coating and high adhesive force, can effectively inhibit the outward migration of Cr element contained in the metal connector for a long time, solves the problem of cathode poisoning, and can reduce Cr2O3The growth rate of the membrane reduces the working resistance of the connector and improves the comprehensive working performance of the stainless steel connector. Meanwhile, the coating material can also be used for a metal bipolar plate of a proton exchange membrane fuel cell, and the corrosion resistance of metal is improved. The raw materials (Ti, Si and C powder) used by the coating are low in price, and Nb, Ta, W and V powder is expensive, but is used for doping, is less in use and is easy to industrially popularize.
Drawings
FIG. 1 is a schematic view showing the structure of an arc ion plating apparatus according to example 1; wherein, 1, a rotating platform; 2. a sample holder; 3. a partition plate; 4. a target material.
FIG. 2 shows an inner layer of TiC and (Ti, W) prepared by arc ion plating in example 13SiC2The surface appearance of the outer coating;
FIG. 3 shows an inner layer of TiC and (Ti, W) prepared by arc ion plating in example 13SiC2The cross-sectional morphology of the outer coating;
FIG. 4 depicts the deposition of TiC inner layer and (Ti, W) for example 13SiC2A surface microstructure diagram of the SUS430 stainless steel connector of the outer coating after oxidation at 800 ℃;
FIG. 5 shows the TiC inner layer and (Ti, Nb) prepared by the magnetron sputtering method of example 23SiC2The surface appearance of the outer coating after oxidation;
FIG. 6 shows an inner layer of TiC and Ti made by the arc ion plating method of example 33SiC2The surface appearance of the outer coating after oxidation.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
The metallic interconnect material used in the following examples is a ferritic stainless steel alloy, commercially available from any of SUS430, Crofer22APU, Fe-10Cr, 1.4724, Fe-17Cr-0.2Y, 1.4016, Ferrotherm (1.4742), Fe-18Cr-9W, Fe-20Cr-7W, Fe-20Cr, AL 453, 1.4763(446), FeCrMn (LaTi), Fe-Cr-Mn, Fe-25Cr-DIN 50049, Fe-25Cr-0.1Y-2.5Ti, Fe-25Cr-0.2Y-1.6Mn, Fe-25Cr-0.4La, Fe-25Cr-0.3Zr, Fe26CrTiY, Fe26CrTiNbY, Fe26CrMoTiY, E-Bri 29-4C, or Fe-30 Cr.
The TiC target material used for deposition is a commercially purchased round block target material or is obtained by a self-made method, and the preparation method comprises the following steps: the original powder comprises Ti powder and graphite powder, and is prepared by sintering in a hot pressing furnace by a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 900-1300 ℃, the temperature is kept for 20-60 minutes, the hot pressing pressure is 10-30 MPa, and flowing argon is used as protective gas. Ti for deposition3SiC2Ceramics and doped modified solid solution material ((Ti, M)3SiC2M is one of Nb, Ta, W and V) target material. The preparation method comprises the following steps: the raw powder comprises Ti powder, silicon powder and graphite powder, the solid solution also comprises any one of Nb powder, Ta powder, W powder and V powder, and the raw powder is prepared by sintering in a hot pressing furnace by a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 1000-1700 ℃, the heat is preserved for 15-60 minutes, the hot pressing pressure is 10-60 MPa, and flowing argon is used as protective gas.
Example 1
Mixing TiC and (Ti, W)3SiC2The coating was deposited on the surface of Crofer22APU stainless steel interconnect. First of all (Ti, W)3SiC2Bulk target, and commercial TiC round target and Crofer22APU stainless steel alloy. The alloy matrix is gradually graded by using 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# metallographic abrasive paperAnd (3) polishing, then respectively ultrasonically cleaning the polished metal connector sample for 15min by acetone, alcohol and deionized water, and then drying the metal connector sample in the air for later use.
And depositing a coating on the surface of the alloy by using an arc ion plating device. The arc ion plating device comprises a rotary table, a partition plate is arranged on the upper surface of the rotary table, the space above the rotary table is divided into a plurality of relatively independent spaces, a sample frame is arranged in the independent spaces, an upright post of the sample frame can rotate, and the upright post can revolve along with the rotary table.
The sample is first suspended on a sample holder of the apparatus (as shown in fig. 1), and the column of the sample holder can rotate while the rotating column can revolve with the rotating table. Before the coating is prepared, the vacuum chamber is pre-vacuumized until the back bottom vacuum is 5 multiplied by 10-3And after Pa, applying 500V negative pulse bias voltage on the substrate to carry out back-splash cleaning on the substrate for 15min, and removing pollutants and an oxidation layer on the surface of the substrate. Then opening an Ar flow valve, wherein the flow rate of Ar gas is 50ml/min, controlling the working air pressure in the vacuum chamber to be maintained at about 0.35Pa by adjusting the pumping speed of the molecular pump, and the heating temperature of the chamber is 500 ℃. And then switching on a TiC target direct-current power supply, wherein the arc current is 70A, the bias voltage is-300V, and the sputtering time is 30 min. After sputtering, the DC power supply to the TiC target is turned off, and then (Ti, W) is turned on3SiC2The target material is provided with a direct current power supply, the arc current is 45A, the bias voltage is-500V, and the sputtering time is 20 min. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped. And finally, observing the surface and section microscopic morphology of the deposited coating by using a scanning electron microscope, wherein the deposited coating is compact and flat, has no holes and is well combined with the matrix, and the thickness of the coating under the condition is about 7 mu m (as shown in figures 2 and 3).
The deposited TiC inner layer and (Ti, W)3SiC2After the Crofer22APU stainless steel connector of the outer coating is oxidized at 600-800 ℃, a compact and continuous oxide film structure (shown in figure 4) is formed on the surface of the Crofer22APU stainless steel connector, and the volatilization of Cr can be effectively blocked, so that the problem of cathode poisoning of an SOFC (solid oxide fuel cell) is solved, and meanwhile, Cr can be reduced2O3The growth rate of the film. While after oxidation, the surface specific resistance of the oxide film was found to be reduced by 25%, indicating that the coating was coatedThe preparation reduces the working resistance of the connector, effectively improves the conductivity of the alloy connector material and improves the comprehensive working performance of the stainless steel connector.
Example 2
Mixing TiC inner layer with (Ti, Nb)3SiC2The outer coating was deposited on the surface of the SUS430 stainless steel interconnect. First, TiC and (Ti, Nb)3SiC2Bulk target material, and commercially available SUS430 stainless steel alloy. And (2) gradually polishing the alloy matrix by using 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# metallographic abrasive paper, then respectively ultrasonically cleaning the polished metal connector sample for 10min by using acetone, alcohol and deionized water, and drying the metal connector sample in the air for later use.
The magnetron sputtering equipment is used for depositing a coating on the surface of the alloy, firstly, a sample is hung on a sample rack of the equipment (shown in figure 1), and a stand column of the sample can rotate, and meanwhile, the rotating stand column can revolve with a rotating table. Before the coating is prepared, firstly, the vacuum is pre-pumped to 5X 10-4Pa to minimize contamination of residual gases during sputtering. After reaching the vacuum degree required by the experiment, high-purity Ar gas with the flow rate of 30ml/min is introduced, and the working air pressure is adjusted to be kept at 0.30 Pa. First using Ar before the start of deposition+And cleaning the target material to remove pollutants on the surface of the target material, wherein the cleaning time is 10 min. The sample was then heated to 400 ℃ and held for 15min to allow the temperature of the entire sample to be uniform before sputtering to produce the coating. In the coating preparation process, firstly, a TiC inner layer is prepared, a TiC target power supply is turned on, the sputtering power is 0.3kw, and the sputtering time is 1 h. Then the TiC target power is turned off and turned on (Ti, Nb)3SiC2Target power, sputtering (Ti, Nb)3SiC2And the outer layer is sputtered at the power of 0.2kw for 5 h. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped. Finally, observing the surface and section microscopic morphology of the deposited coating by using a scanning electron microscope, and finding a TiC inner layer and (Ti, Nb)3SiC2The outer coating is compact and smooth, has no holes, and is well combined with the matrix, and the thickness of the coating under the condition is about 5.5 mu m.
In the deposited TiCLayer sum (Ti, Nb)3SiC2After the SUS430 stainless steel connector with the outer coating is oxidized at 800 ℃ for 100 hours, a compact oxide film (shown in figure 5) is formed on the surface of the SUS430 stainless steel connector, the volatilization of Cr can be effectively prevented, meanwhile, after the oxidation, the surface specific resistance of the oxide film is reduced by 19% compared with that of the alloy without the coating, the working resistance of the connector is reduced by the preparation of the coating, and the comprehensive working performance of the alloy connector is effectively improved.
Example 3
Mixing TiC inner layer and Ti3SiC2The outer layer was deposited on the surface of AL 453 stainless steel interface. First, Ti is prepared3SiC2Bulk target and TiC target, and commercially available AL 453 stainless steel alloy. And (2) gradually polishing the alloy matrix by using 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# metallographic abrasive paper, then respectively ultrasonically cleaning the polished metal connector sample for 15min by using acetone, alcohol and deionized water, and drying the metal connector sample in the air for later use.
The arc ion plating equipment is used for depositing a coating on the surface of the alloy, firstly, a sample is hung on a sample rack of the equipment (shown in figure 1), and a stand column of the sample can rotate, and meanwhile, the rotating stand column can revolve along with the rotating table. Before the coating is prepared, the vacuum chamber is pre-vacuumized until the back bottom vacuum is 5 multiplied by 10-3And after Pa, applying 500V negative pulse bias voltage on the substrate to carry out back-splash cleaning on the substrate for 15min, and removing pollutants and an oxidation layer on the surface of the substrate. Then opening an Ar flow valve, wherein the flow rate of Ar gas is 50ml/min, controlling the working air pressure in the vacuum chamber to be maintained at about 0.35Pa by adjusting the pumping speed of the molecular pump, and the heating temperature of the chamber is 400 ℃. And then switching on a TiC target direct-current power supply, wherein the arc current is 50A, the bias voltage is-300V, and the sputtering time is 20 min. And after sputtering, closing the direct current power supply of the TiC target. Then heating the chamber to 700 ℃, keeping the temperature for 15min, and opening Ti3SiC2The target material is provided with a direct current power supply, the arc current is 35A, the bias voltage is-500V, and the sputtering time is 40 min. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped. Finally, observing the surface and section microscopic morphology of the deposited coating by using a scanning electron microscope, and finding that the double-layer coating is compact and flat, has no holes and is matched with the matrix after depositionThe bonding was good. After the coating is oxidized at 800 ℃, a dense and continuous oxide film structure is formed on the surface (as shown in fig. 6), which can effectively block the volatilization of Cr, thereby solving the problem of SOFC cathode poisoning.
Example 4:
mixing TiC inner layer with (Ti, V)3SiC2The outer coating was deposited on the surface of the 316L stainless steel interconnect. First of all (Ti, V)3SiC2Bulk target, and commercial TiC round target and 316L stainless steel alloy were purchased. And (2) gradually polishing the alloy matrix by using 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# metallographic abrasive paper, then respectively ultrasonically cleaning the polished metal connector sample for 20min by using acetone, alcohol and deionized water, and drying the metal connector sample in the air for later use.
The magnetron sputtering equipment is used for depositing a coating on the surface of the alloy, firstly, a sample is hung on a sample rack of the equipment (shown in figure 1), and a stand column of the sample can rotate, and meanwhile, the rotating stand column can revolve with a rotating table. Before the coating is prepared, firstly, the vacuum is pre-pumped to 5X 10-4Pa to minimize contamination of residual gases during sputtering. After reaching the vacuum degree required by the experiment, high-purity Ar gas with the flow rate of 30ml/min is introduced, and the working air pressure is adjusted to be kept at 0.35 Pa. First using Ar before the start of deposition+And cleaning the target to remove pollutants on the surface of the target, wherein the cleaning time is 20 min. The sample was then heated to 200 ℃ and held for 15min to allow the temperature of the entire sample to be uniform before sputtering to produce the coating. In the coating preparation process, firstly, a TiC inner layer is prepared, a TiC target power supply is turned on, the sputtering power is 0.4kw, and the sputtering time is 2 h. Then the TiC target power is turned off and (Ti, V) is turned on3SiC2Target power supply, sputtering (Ti, V)3SiC2And the outer layer is sputtered at the power of 0.5kw for 3 h. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped.
After the experiment, the microscopic appearance of the surface and the section of the deposited coating is observed by using a scanning electron microscope, and after the deposition, the double-layer coating is found to be compact and flat, has no holes and is well combined with the matrix. In a simulated fuel cell simulation environment (H)2SO4Concentration of0.5mol/L at a temperature of 70 ℃) and shows that the corrosion current density after the bipolar plate is deposited with a coating is 12 mu A/cm2[ Corrosion potential 0.075V (vs. SCE)]The assembling force is 150N/cm2Under the condition, the contact resistance is 6.5m omega cm2Therefore, the coating can effectively improve the corrosion resistance and the conductivity of the bipolar plate of the proton exchange membrane fuel cell.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (9)
1. The double-layer coating of the metal connector of the fuel cell is characterized in that the outer layer of the double-layer coating is Ti3SiC2Or doping modified solid solution material (Ti, M)3SiC2Wherein M is selected from one of Nb, Ta, W and V materials, and the inner layer is a TiC layer.
2. The metal interconnect bi-layer coating of claim 1, wherein the metal interconnect bi-layer coating is deposited on the surface of the metal interconnect by a method comprising: pretreating the metal connector; with Ti3SiC2Or doping modified solid solutions (Ti, M)3SiC2The target material block is an outer coating target material block, and M is any one of Nb, Ta, V or W; the TiC block is used as the target material of the TiC layer as the inner layer, and the target material is deposited on the surface of the metal connector by adopting a magnetron sputtering method or an arc ion plating method in the preparation of the double-layer coating.
3. The metal interconnect coating of claim 2, wherein the metal interconnect is a ferritic stainless steel: any one of SUS430, Crofer22APU, Fe-10Cr, 1.4724, Fe-17Cr-0.2Y, 1.4016, Ferrotherm (1.4742), Fe-18Cr-9W, Fe-20Cr-7W, Fe-20Cr, AL 453, 1.4763(446), FeCrMn (LaTi), Fe-Cr-Mn, Fe-25Cr-DIN 50049, Fe-25Cr-0.1Y-2.5Ti, Fe-25Cr-0.2Y-1.6Mn, Fe-25Cr-0.4La, Fe-25Cr-0.3Zr, Fe26CrTiY, Fe26CrTiNbY, Fe26CrMoTiY, E-Brite, Al29-4C or Fe-30 Cr.
4. The metal interconnect coating of claim 2, wherein the Ti3SiC2Ceramic or doped modified solid solution bulk material (Ti, M)3SiC2The preparation method comprises the following steps: the raw powder comprises Ti powder, silicon powder and graphite powder, the solid solution also comprises any one of Nb powder, Ta powder, W powder and V powder, and the raw powder is prepared by sintering in a hot pressing furnace by a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 1000-1700 ℃, the heat is preserved for 15-60 minutes, the hot pressing pressure is 10-60 MPa, and flowing argon is used as protective gas. The TiC target is a commercially purchased round block target or is obtained by a self-made method, and the preparation method comprises the following steps: the original powder is Ti powder and graphite powder, and is prepared by sintering in a hot pressing furnace by a hot pressing/solid-liquid phase reaction method, wherein the sintering temperature is 900-1300 ℃, the temperature is kept for 20-60 minutes, the hot pressing pressure is 10-30 MPa, and flowing argon is used as protective gas.
5. The metal interconnect coating of claim 2, wherein the coating is deposited on the surface of the alloy by an arc ion plating apparatus or a magnetron sputtering apparatus, wherein the sample is suspended on a sample holder of the apparatus during the deposition of the coating, and the rotating column for suspending the sample is rotatable while the rotating column is rotatable around a rotating table, thereby obtaining a uniform coating.
6. The metal interconnect coating of claim 2, wherein the metal interconnect is pretreated by: firstly, sand paper is selected to polish and polish the metal connector, namely, metallographic sand paper of 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000# is used for polishing step by step, then the polished metal connector sample is subjected to ultrasonic cleaning for 5-30 min by acetone, alcohol and deionized water respectively, and then is dried in the air for later use.
7. The method of claim 2The metal connector double-layer coating is characterized in that the vacuum chamber is pre-vacuumized to the back bottom vacuum of 5 multiplied by 10 before the coating is prepared by the arc ion plating method-3And after Pa, applying 500V negative pulse bias voltage on the substrate to carry out back-splash cleaning on the substrate for 5-15 min, and removing pollutants and an oxidation layer on the surface of the substrate. Then opening the Ar flow valve, wherein the Ar gas flow is 50ml/min, and controlling the working air pressure in the vacuum chamber by adjusting the pumping speed of the molecular pump to maintain the working air pressure at 0.30-0.40Pa and the heating temperature of the chamber at 300-500 ℃. Firstly, a TiC coating is deposited, namely a direct-current power supply is turned on, the arc current is 50-80A, the bias voltage is-300-400V, and the sputtering time is 10-30 min. Then depositing an outer layer of Ti3SiC2Or doping modified solid solution material (Ti, M)3SiC2(M ═ Nb, Ta, V or W), adjusting the temperature of the chamber to 200-700 ℃, preserving the temperature for 15min, then turning on a direct current power supply, wherein the arc current is 30-70A, the bias voltage is-400-500V, and the sputtering time is 10-60 min. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped.
8. The metal interconnect coating of claim 2, wherein said magnetron sputtering process is preceded by a preliminary vacuum of 5 x 10 prior to coating preparation-4Pa to minimize contamination of residual gases during sputtering. And introducing high-purity Ar gas with the flow rate of 30ml/min after the vacuum degree required by the experiment is reached, and adjusting the working air pressure to be kept at 0.25-0.35 Pa. First using Ar before the start of deposition+And cleaning the target to remove pollutants on the surface of the target, wherein the cleaning time is 5-15 min. And then heating the sample to 100-800 ℃, and preserving heat for 15min to ensure that the temperature of the whole sample is uniform and then starting sputtering to prepare the coating. In the coating preparation process, firstly, the TiC inner layer is prepared, the sputtering power is 0.1-2.5 kw, and the sputtering time is 1-2 h. Then sputtering an outer Ti layer3SiC2Or doping modified solid solution material (Ti, M)3SiC2(M ═ Nb, Ta, V or W), the sputtering power is 0.1 to 2.5kw, and the sputtering time is 1 to 6 hours. After deposition is finished, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then vacuumizing and pressure removing are stopped.
9. A metal interconnect for a fuel cell, characterized in that it has a two-layer coating according to claim 1.
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