CN115548364A - Corrosion-resistant conductive metal bipolar plate and preparation method thereof - Google Patents
Corrosion-resistant conductive metal bipolar plate and preparation method thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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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
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- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- H—ELECTRICITY
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- 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
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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
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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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
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- 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 discloses a corrosion-resistant conductive metal bipolar plate and a preparation method thereof, wherein the corrosion-resistant conductive metal bipolar plate comprises a metal substrate and a coating, the coating is deposited on the surface of the metal substrate, the coating comprises a metal system consisting of five metal elements of Fe, co, cr, ni and Al and graphene, and the content of the graphene is 1-3wt% of that of the metal system; wherein, in the metal system, the content of Fe element is 15-20wt%, the content of Co element is 14-20wt%, the content of Cr element is 20-32wt%, the content of Ni element is 20-32wt%, and the content of Al element is 19-26wt%. The technical scheme of the invention adopts the graphene modified FeCoCrN iA l high-entropy alloy coating, and the modified coating is applied to the metal bipolar plate, so that the corrosion resistance of the metal bipolar plate is greatly improved, and the contact resistance of the metal bipolar plate is reduced.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a corrosion-resistant conductive metal bipolar plate and a preparation method thereof.
Background
In general, bipolar Plates (BP) are considered as a key component of Proton Exchange Membrane Fuel Cells (PEMFC), which account for around 40% of the cost of PEMFC. In particular, the bipolar plate ensures mechanical strength of the PEMFC stack, collects current generated during electrochemical reaction, prevents gas leakage, and separates fuel and oxidant gases. The types of bipolar plates mainly developed at present are metal bipolar plates, composite bipolar plates and graphite bipolar plates. The metal bipolar plate has good electrical conductivity, thermal conductivity, gas barrier property and machining performance, the thickness of the metal bipolar plate can reach 0.07-0.1 mm, and the volume of a high-power metal plate galvanic pile is smaller than that of a graphite plate galvanic pile and the power density is higher, so that the metal bipolar plate is highly bright in the field of vehicular galvanic piles. However, it is not negligible that the metal plate will release metal ions that poison the catalyst after corrosion, or form a dense oxide film that increases the interfacial contact resistance, which will result in a large reduction in the output and service life of the fuel cell. Therefore, it is important to develop a metal bipolar plate having high corrosion resistance and low interfacial contact resistance.
The most effective strategy for dealing with a reasonable match of conductivity to corrosion resistance is currently to modify the surface coating of the metal plate, the design of the coating material composition playing a key role. The high-entropy alloy breaks through the traditional alloy design concept, and becomes one of the research hotspots in the field of metal materials due to the high-entropy effect, the lattice distortion effect, the delayed diffusion effect, the cocktail effect and the like.
The above is only for the purpose of assisting understanding of the technical solutions of the present invention, and does not represent an admission that the above is the prior art.
Disclosure of Invention
The invention mainly aims to provide a corrosion-resistant conductive metal bipolar plate and a preparation method thereof, and aims to improve the corrosion resistance of the metal bipolar plate and reduce the interface contact resistance of the metal bipolar plate.
In order to achieve the above object, the present invention provides a corrosion-resistant conductive metal bipolar plate, comprising:
a metal substrate;
the coating is deposited on the surface of the metal substrate and comprises a metal system consisting of five metal elements of Fe, co, cr, ni and Al and graphene, wherein the content of the graphene is 1-3wt% of that of the metal system; wherein, the first and the second end of the pipe are connected with each other,
in the metal system, the content of Fe element is 15-20wt%, the content of Co element is 14-20wt%, the content of Cr element is 20-32wt%, the content of Ni element is 20-32wt%, and the content of Al element is 19-26wt%.
In one embodiment, the coating has a thickness of 0.4-0.6mm.
The invention also provides a preparation method of the corrosion-resistant conductive metal bipolar plate, which comprises the following steps:
s1: screening five kinds of metal simple substance powder of Fe, co, cr, ni and Al and graphene powder which meet the requirement of granularity;
s2: uniformly mixing the powder of five simple metal substances of Fe, co, cr, ni and Al screened in the S1 and graphene powder according to a certain proportion to obtain mixed powder, wherein the powder of five simple metal substances of Fe, co, cr, ni and Al in the mixed powder forms a metal system, the content of Fe element in the metal system is 15-20wt%, the content of Co element in the metal system is 14-20wt%, the content of Cr element in the metal system is 20-32wt%, the content of Ni element in the metal system is 20-32wt%, the content of Al element in the metal system is 19-26wt%, and the content of graphene is 1-3wt% of the total content of the metal system;
s3: performing ball milling treatment and drying treatment on the mixed powder in sequence to obtain dried powder;
s4: and depositing the dried powder on the surface of a metal substrate to prepare the corrosion-resistant conductive metal bipolar plate.
In an embodiment, in S4, the dried powder is deposited on the surface of the metal substrate by thermal spraying, bead welding or laser deposition.
In an embodiment, in S4, the dried powder is directly deposited on the surface of the metal substrate by a laser metal deposition method, which includes the following specific steps:
and conveying the dried powder to the surface of a metal substrate by using a powder conveying device, and melting and depositing the dried powder on the surface of the metal substrate by using a laser with certain power under the atmosphere of protective gas to obtain the corrosion-resistant conductive metal bipolar plate.
In one embodiment, the powder feeding speed of the powder feeding device is 5-8g/min, and the flow rate of the carrier gas is 4-6L/min.
In one embodiment, the laser power of the laser is 800-1000W, and the laser scanning speed is 5-7 mm/min.
In one embodiment, in the S1, the particle size range of the selected five elemental metal powders of Fe, co, cr, ni, and Al is 140-300 mesh.
In one embodiment, in the step S3, the rotation speed of the ball mill during the ball milling treatment is 100 to 200r/min, and the ball milling time is 1.5 to 3 hours;
and/or the drying temperature in the drying treatment process is 30-50 ℃, and the drying time is 1-2h.
In one embodiment, in the S1, the purity of the screened elemental powders of five metals, i.e., fe, co, cr, ni, and Al, is not less than 99.9%.
According to the technical scheme, the graphene modified FeCoCrNiAl high-entropy alloy coating is adopted, and the modified coating is applied to the metal bipolar plate, so that the corrosion resistance of the metal bipolar plate is greatly improved, and the contact resistance of the metal bipolar plate is reduced. In the technical scheme of the invention, a high-entropy alloy system with excellent corrosion resistance is constructed by combining Fe, co, cr, ni and Al metal elements in a proper proportion; in addition, the graphene with excellent corrosion resistance and conductivity is doped into the high-entropy alloy system in a proper proportion, so that the corrosion resistance of the high-entropy alloy system is further improved, and the conductivity of the high-entropy alloy system is improved, so that the prepared coating realizes 'double harvest' of corrosion resistance and conductivity; according to the invention, a small amount of graphene is doped into the high-entropy alloy system to be prepared into the coating deposited on the metal substrate, so that the corrosion resistance and the conductivity of the metal bipolar plate are improved, and the durability and the electrochemical performance of the prepared fuel cell are further improved.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method of making a corrosion-resistant, electrically-conductive metallic bipolar plate according to the present invention;
fig. 2 is a schematic structural view of an apparatus for manufacturing a corrosion-resistant conductive metallic bipolar plate according to an embodiment of the present invention.
The reference numbers illustrate:
the implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications (such as upper, lower, left, right, front, rear, 8230; \8230;) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative positional relationship between the components in a specific posture (as shown in the figure), the motion situation, etc., and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description relating to "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, if appearing throughout the text, "and/or" is meant to include three juxtaposed aspects, taking "a and/or B" as an example, including either the a aspect, or the B aspect, or both the a and B aspects. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass non-exclusive inclusions, as well as non-exclusive distinctions between such terms. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting essentially of and" consisting essentially of "〓 and" consisting essentially of "\\8230". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified. Unless otherwise defined, terms used in the present specification have the same meaning as those generally understood by those skilled in the art, but in case of conflict, the definitions in the present specification shall control.
In the beginning of the 21 st century, professor yeasts the concept of "multicomponent high-entropy alloy", which is an alloy consisting of five or more main elements with equal atomic ratio or near equal atomic ratio and has a simple crystal structure. The high-entropy alloy has excellent properties of high strength, high hardness, wear resistance, corrosion resistance, high-temperature oxidation resistance and the like; the high-entropy alloy breaks through the traditional alloy design idea that one or two elements playing key roles are used as components and other elements playing auxiliary roles are used for modifying the performance; the high entropy effect enables the formation of a homogeneous single face-centered cubic structure or a disordered solid solution phase of a body-centered cubic structure, inhibiting the formation of complex structural phases which seriously affect the quality and the service performance of the coating.
The graphene serving as a two-dimensional carbon nanomaterial has the characteristics of excellent physical properties, stable chemical properties, impermeability of a complete structure to oxygen and water, and high length-to-length ratio. Graphene from Sp 2 The hybridized carbon atom is composed of hybridized carbon atoms, the electron density of the hybridized carbon atoms on an aromatic ring is high, all molecules can be blocked, and the special structure of graphene enables the graphene to have impermeability. The laminated structure of the graphene stack blocks the contact of water, gas, corrosive substances and the like with a metal matrix, provides good shielding protection by prolonging a permeation path, and has hydrophobicity, so that a good physical anti-corrosion effect is achieved. In addition, the graphene has excellent conductivity, and can prevent electrochemical corrosion.
Based on the structure, the invention provides a corrosion-resistant conductive metal bipolar plate.
In the embodiment of the invention, the corrosion-resistant conductive metal bipolar plate comprises a metal substrate and a coating, wherein the coating is deposited on the surface of the metal substrate, the coating comprises a metal system consisting of five metal elements of Fe, co, cr, ni and Al and graphene, and the content of the graphene is 1-3wt% of that of the metal system; wherein, in the metal system, the content of Fe element is 15-20wt%, the content of Co element is 14-20wt%, the content of Cr element is 20-32wt%, the content of Ni element is 20-32wt%, and the content of Al element is 19-26wt%.
According to the corrosion-resistant conductive metal bipolar plate, the content of the graphene is 1wt%, 2wt%, 3wt% or any value between the two of the contents of the metal system. On the basis of the metal system, the corrosion resistance of the metal bipolar plate is weakened and the contact resistance of the metal bipolar plate is improved due to the fact that the content of the graphene is too high or too low.
According to the corrosion-resistant conductive metal bipolar plate, the metal system consists of a high-purity Fe simple substance, a Co simple substance, a Cr simple substance, a Ni simple substance and an Al simple substance, and the purity of each metal simple substance is not less than 99.9%. In the metal system, the content of Fe element is 15wt%, 18wt%, 20wt% or any value therebetween, the content of Co element is 14 wt%, 18wt%, 20wt% or any value therebetween, the content of Cr element is 20wt%, 25 wt%, 32wt% or any value therebetween, the content of Ni element is 20wt%, 28 wt%, 32wt% or any value therebetween, and the content of Al element is 19 wt%, 23 wt%, 26wt% or any value therebetween; within the content range, the corrosion-resistant conductive metal bipolar plate has stronger corrosion resistance and lower contact resistance.
According to the corrosion-resistant conductive metal bipolar plate of the present invention, the thickness of the coating is 0.4-0.6mm, i.e., the thickness of the coating is 0.4mm, 0.5mm, 0.6mm or any value therebetween. Within the thickness range, the corrosion-resistant conductive metal bipolar plate has ideal corrosion resistance and conductivity, and also has good heat conductivity, gas barrier property, machinability and other properties.
According to the technical scheme, the graphene modified FeCoCrNiAl high-entropy alloy coating is adopted, and the modified coating is applied to the metal bipolar plate, so that the corrosion resistance of the metal bipolar plate is greatly improved, and the contact resistance of the metal bipolar plate is reduced. According to the technical scheme, a high-entropy alloy system with excellent corrosion resistance is constructed by combining Fe, co, cr, ni and Al metal elements in a proper proportion; in addition, graphene with excellent corrosion resistance and conductivity is doped into the high-entropy alloy system in a proper proportion, so that the corrosion resistance of the high-entropy alloy system is further improved, the conductivity of the high-entropy alloy system is improved, and the prepared coating realizes 'double harvest' of corrosion resistance and conductivity; according to the invention, a small amount of graphene is doped into the high-entropy alloy system to form the coating deposited on the metal substrate, so that the corrosion resistance and the conductivity of the metal bipolar plate are improved, and the durability and the electrochemical performance of the prepared fuel cell are further improved.
Referring to fig. 1, the present invention further provides a method for manufacturing the corrosion-resistant conductive metal bipolar plate, comprising the following steps:
s1: screening out five kinds of elemental metal powder of Fe, co, cr, ni and Al and graphene powder which meet the requirement of granularity.
In the S1, the purity of the screened five metal simple substance powders of Fe, co, cr, ni and Al is not lower than 99.9%.
S2: uniformly mixing the five elementary metal powders of Fe, co, cr, ni and Al screened from the S1 and graphene powder according to a certain proportion to obtain mixed powder, wherein the five elementary metal powders of Fe, co, cr, ni and Al in the mixed powder form a metal system, the content of Fe element in the metal system is 15-20wt%, the content of Co element in the metal system is 14-20wt%, the content of Cr element in the metal system is 20-32wt%, the content of Ni element in the metal system is 20-32wt%, the content of Al element in the metal system is 19-26wt%, and the content of graphene is 1-3wt% of the total content of the metal system.
S3: performing ball milling treatment and drying treatment on the mixed powder in sequence to obtain dried powder; and performing the ball milling treatment to further uniformly mix the metal simple substance powder and the graphene powder in the mixed powder, and removing moisture in the mixed powder through the drying treatment.
In S3, the ball milling rotating speed in the ball milling treatment process is 100-200r/min, and the ball milling time is 1.5-3h; and/or the drying temperature in the drying treatment process is 30-50 ℃, and the drying time is 1-2h. In one embodiment, the mixed powder is ball milled using a planetary ball mill and an agate jar.
S4: and depositing the dried powder on the surface of a metal substrate to prepare the corrosion-resistant conductive metal bipolar plate.
According to the preparation method of the corrosion-resistant conductive metal bipolar plate, five kinds of metal simple substance powder of Fe, co, cr, ni and Al and graphene powder are mixed in a proper proportion and are simultaneously deposited on the surface of a metal substrate, so that the graphene modified FeCoCrNiAl high-entropy alloy coating deposited on the metal substrate is prepared, and the modified coating has excellent corrosion resistance and conductivity at the same time, so that the prepared metal bipolar plate is 'double-harvest' with high corrosion resistance and high conductivity. In the preparation method, fe, co, cr, ni and Al metal powder in a proper proportion are combined together to construct a high-entropy alloy system with excellent corrosion resistance; the graphene with excellent corrosion resistance and conductivity is doped into the high-entropy alloy system in a proper proportion, so that the corrosion resistance of the high-entropy alloy system can be further improved, and the conductivity of the high-entropy alloy system can be improved at the same time. The preparation method of the corrosion-resistant conductive metal bipolar plate can prepare the metal bipolar plate with excellent corrosion resistance and conductivity, has simple and reliable preparation process and is beneficial to commercialization.
According to the method for preparing the corrosion-resistant conductive metal bipolar plate of the present invention, in S4, the dried powder may be deposited on the surface of the metal substrate by thermal spraying, bead welding, or laser deposition, or by other methods known to those skilled in the art.
In an embodiment, it is preferable that, in S4, the dried powder is directly deposited on the surface of the metal substrate by a laser metal deposition method, and the specific steps include: and conveying the dried powder to the surface of a metal substrate by using a powder conveying device, and melting and depositing the dried powder on the surface of the metal substrate by using a laser with certain power under the atmosphere of protective gas to obtain the corrosion-resistant conductive metal bipolar plate. The protective gas is generally selected from inert gases,
the laser metal deposition technology utilizes a laser beam with high energy density to fuse the cladding material and a thin layer on the surface of the base material together, and an alloy layer with more excellent performance is formed on the surface of the base material. Compared with other surface deposition techniques, the laser metal deposition technique has the advantages of small heat influence on the metal matrix, metallurgical bonding between the coating and the metal matrix, low coating dilution rate (generally less than 5%), fine and uniform microstructure, wide selection range of cladding powder, selective cladding, low material consumption and the like. And depositing the dried powder on the surface of the metal matrix by using a laser metal deposition technology, so that the adhesive force of the coating on the surface of the metal matrix is enhanced.
In one embodiment, the powder feeding device is a coaxial powder feeding device, the powder feeding speed of the powder feeding device is 5-8g/min, and the flow rate of carrier gas is 4-6L/min. The laser device is a semiconductor laser device, a laser spot is circular, the diameter is 2-4 mm, the laser power of the laser device is 800-1000W, and the laser scanning speed is 5-7 mm/min.
In the step S1, the particle size range of the screened Fe, co, cr, ni and Al metal elementary powder and graphene powder is 140-300 meshes, and in the particle size range, the dried powder can meet the requirement of a laser deposition technology on the particle size of a cladding material.
In one embodiment, the apparatus shown in fig. 2 is used to prepare the corrosion-resistant conductive metal bipolar plate, and the apparatus includes a machine tool and control system 20, an LDM2500-60 semiconductor laser 10, a powder feeding device 30, a fixed table 70, a coaxial table 40 and a detection sensor 50, during the preparation process, a metal substrate 60 is placed on the table 70, the dried powder is fed to the surface of the metal substrate through the powder feeding device 30 and the coaxial table 40, and the machine tool and control system 20 controls the LDM2500-60 semiconductor laser 10 to emit laser to the metal substrate 60 located in the laser action region, so that the powder is deposited on the surface of the metal substrate 60; the detection sensor 50 is used for detecting whether the deposition track of the powder on the metal substrate 60 is correct; in order to avoid the oxidation of the elemental metal powder, the powder feeding process and the laser action process are both performed under the atmosphere of the protective gas 80, the inert gas 81 is generally selected as the protective gas 80, and in an embodiment, the inert gas 81 is helium.
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1: screening out Fe, co, cr, ni and Al elemental metal powder and graphene (Gr) powder with the particle size of 140-300 meshes by using a screen;
s2: the screened five metal simple substance powders of Fe, co, cr, ni and Al are mixed according to the mass ratio of 15:14:25:25:21, mixing; and mixing the graphene powder into the five metal simple substance powder according to the feeding amount of 2% of the total mass of the five metal simple substance powder of Fe, co, cr, ni and Al to obtain mixed powder.
S3: placing the mixed powder into a planetary ball mill for ball milling, and adopting an agate ball milling tank, wherein the ball milling time is 2 hours, and the ball milling rotating speed is 150r/min; then drying at the constant temperature of 50 ℃ for 1.5 hours to obtain dried powder.
S4: and (2) conveying the dried powder to the surface of a metal substrate of a laser action area by adopting a coaxial powder conveying device at a powder conveying speed of 6g/min and a carrier gas flow rate of 5L/min, and melting and depositing the dried powder on the surface of the metal substrate by using a laser with a laser power of 800W and a laser scanning speed of 6mm/min under the protection of argon gas to obtain the corrosion-resistant conductive metal bipolar plate.
Example 2
Example 2 differs from example 1 only in that: the screened five metal simple substance powders of Fe, co, cr, ni and Al are mixed according to the mass ratio of 20:14:23:23:20 were mixed and the manufacturing method was referred to example 1, to obtain a corrosion-resistant conductive metallic bipolar plate of example 2.
Example 3
Example 3 differs from example 1 only in that: screening five metal simple substance powders of Fe, co, cr, ni and Al according to the mass ratio of 15:20:23:22:20 were mixed and the manufacturing method was referred to example 1, to obtain a corrosion-resistant conductive metallic bipolar plate of example 3.
Example 4
Example 4 differs from example 1 only in that: screening five metal simple substance powders of Fe, co, cr, ni and Al according to the mass ratio of 15:14:32:20:19 mixing, method of making reference to example 1, a corrosion resistant conductive metallic bipolar plate of example 1 was obtained.
Example 5
Example 5 differs from example 1 only in that: screening five metal simple substance powders of Fe, co, cr, ni and Al according to the mass ratio of 15:14:20:32:19 mixing, method of making reference to example 1, a corrosion resistant conductive metallic bipolar plate of example 5 was obtained.
Example 6
Example 6 differs from example 1 only in that: the screened five metal simple substance powders of Fe, co, cr, ni and Al are mixed according to the mass ratio of 15:14:23:22:26 mixing, preparation method referring to example 1, a corrosion-resistant conductive metal bipolar plate of example 3 was obtained.
Example 7
Example 7 differs from example 1 only in that: the graphene powder is mixed into five kinds of metal simple substance powder according to the feeding amount of 1% of the total mass of the five kinds of metal simple substance powder of Fe, co, cr, ni and Al, the preparation method refers to example 1, and the corrosion-resistant conductive metal bipolar plate of example 7 is obtained.
Example 8
Example 8 differs from example 1 only in that: the graphene powder is mixed into five kinds of metal simple substance powder together according to the feeding amount of 3% of the total mass of the five kinds of metal simple substance powder of Fe, co, cr, ni and Al, and the preparation method refers to example 1, so that the corrosion-resistant conductive metal bipolar plate of example 8 is obtained.
Comparative example 1
Comparative example 1 differs from example 1 only in that: in step S2, the metal bipolar plate of comparative example 1 was obtained by the preparation method of reference example 1 without adding the graphene powder and mixing with the five elemental metal powders of Fe, co, cr, ni, and Al.
Comparative example 2
Comparative example 2 differs from example 1 only in that: the graphene powder is mixed into the five metal simple substance powders according to the feeding amount of 10 percent of the total mass of the five metal simple substance powders of Fe, co, cr, ni and Al, the preparation method refers to the example 1, and the metal bipolar plate of the comparative example 2 is obtained.
Comparative example 3
Comparative example 3 differs from example 1 only in that: the screened five metal simple substance powders of Fe, co, cr, ni and Al are mixed according to the mass ratio of 5:15:26:25:27 were mixed and the manufacturing method was referenced to example 1, to obtain a metallic bipolar plate of comparative example 3.
Comparative example 4
Comparative example 4 differs from example 1 only in that: the screened five metal simple substance powders of Fe, co, cr, ni and Al are mixed according to the mass ratio of 12:12:45:15:16, and preparation method reference example 1, a metallic bipolar plate of comparative example 4 was obtained.
Performance test
The conductive and corrosion resistance properties of the metallic bipolar plates prepared in the respective examples and comparative examples are shown in the following table:
it can be seen from the comparison between example 1 and comparative examples 1-4 that the corrosion resistance and conductivity of the metal bipolar plate can be impaired by the excessive or insufficient contents of the five elemental metal powders of Fe, co, cr, ni and Al and the graphene powder; as can be seen from the above table, the corrosion-resistant conductive metal bipolar plate of the present invention has excellent corrosion resistance and electrical conductivity.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A corrosion resistant conductive metallic bipolar plate comprising:
a metal substrate;
the coating is deposited on the surface of the metal substrate and comprises a metal system consisting of five metal elements of Fe, co, cr, ni and Al and graphene, wherein the content of the graphene is 1-3wt% of that of the metal system; wherein the content of the first and second substances,
in the metal system, the content of Fe element is 15-20wt%, the content of Co element is 14-20wt%, the content of Cr element is 20-32wt%, the content of Ni element is 20-32wt%, and the content of Al element is 19-26wt%.
2. The corrosion-resistant, electrically conductive metallic bipolar plate of claim 1, wherein said coating has a thickness of 0.4 to 0.6mm.
3. A method of manufacturing a corrosion-resistant conductive metallic bipolar plate according to claim 1 or 2, comprising the steps of:
s1: screening five kinds of metal simple substance powder of Fe, co, cr, ni and Al and graphene powder which meet the requirement of granularity;
s2: uniformly mixing the powder of five simple metal substances of Fe, co, cr, ni and Al screened in the S1 and graphene powder according to a certain proportion to obtain mixed powder, wherein the powder of five simple metal substances of Fe, co, cr, ni and Al in the mixed powder forms a metal system, the content of Fe element in the metal system is 15-20wt%, the content of Co element in the metal system is 14-20wt%, the content of Cr element in the metal system is 20-32wt%, the content of Ni element in the metal system is 20-32wt%, the content of Al element in the metal system is 19-26wt%, and the content of graphene is 1-3wt% of the total content of the metal system;
s3: performing ball milling treatment and drying treatment on the mixed powder in sequence to obtain dried powder;
s4: and depositing the dried powder on the surface of a metal substrate to prepare the corrosion-resistant conductive metal bipolar plate.
4. The method of manufacturing a corrosion-resistant conductive metallic bipolar plate according to claim 3, wherein the dried powder is deposited on the surface of the metal substrate by thermal spraying, bead welding or laser deposition in S4.
5. The method of claim 4, wherein in step S4, the dried powder is directly deposited on the surface of the metal substrate by a laser metal deposition method, and the method comprises the following steps:
and conveying the dried powder to the surface of a metal substrate by using a powder conveying device, and melting and depositing the dried powder on the surface of the metal substrate by using a laser with certain power under the atmosphere of protective gas to obtain the corrosion-resistant conductive metal bipolar plate.
6. The method of claim 5, wherein the powder feeding speed of the powder feeding device is 5-8g/min, and the carrier gas flow rate is 4-6L/min.
7. The method of manufacturing a corrosion-resistant conductive metallic bipolar plate according to claim 5, wherein the laser power of the laser is 800-1000W and the laser scanning speed is 5-7 mm/min.
8. The method of claim 5, wherein the grain size of the selected elementary powders of Fe, co, cr, ni and Al in S1 is 140-300 mesh.
9. The method of manufacturing a corrosion-resistant conductive metallic bipolar plate according to claim 3, wherein in the step S3, the rotation speed of the ball mill during the ball milling process is 100 to 200r/min, and the ball milling time is 1.5 to 3 hours;
and/or the drying temperature in the drying treatment process is 30-50 ℃, and the drying time is 1-2h.
10. The method of manufacturing a corrosion-resistant conductive metallic bipolar plate according to any one of claims 3 to 9, wherein the purity of the screened elemental powders of Fe, co, cr, ni, and Al in S1 is not less than 99.9%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116140613A (en) * | 2023-02-07 | 2023-05-23 | 深圳市氢蓝时代动力科技有限公司 | Corrosion-resistant conductive coating material for metal bipolar plate and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828139A (en) * | 2012-09-28 | 2012-12-19 | 安徽工业大学 | High-entropy alloy powder used for spraying |
| CN104350637A (en) * | 2012-05-28 | 2015-02-11 | 株式会社中山非晶质 | Thin plate having excellent corrosion resistance, electroconductivity, and moldability, and method for manufacturing same |
| CN108893738A (en) * | 2018-08-07 | 2018-11-27 | 华东交通大学 | A kind of superhard Fe-Ni based alloy wear-resistant coating of equiax crystal and preparation method thereof |
| CN114023986A (en) * | 2021-09-28 | 2022-02-08 | 上海治臻新能源股份有限公司 | Composite coating for fuel cell titanium substrate bipolar plate and preparation method thereof |
| US20220102737A1 (en) * | 2020-09-28 | 2022-03-31 | Hyzon Motors Inc. | Enhanced durability of fuel cell metallic bipolar plate |
-
2022
- 2022-09-02 CN CN202211070269.8A patent/CN115548364A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104350637A (en) * | 2012-05-28 | 2015-02-11 | 株式会社中山非晶质 | Thin plate having excellent corrosion resistance, electroconductivity, and moldability, and method for manufacturing same |
| CN102828139A (en) * | 2012-09-28 | 2012-12-19 | 安徽工业大学 | High-entropy alloy powder used for spraying |
| CN108893738A (en) * | 2018-08-07 | 2018-11-27 | 华东交通大学 | A kind of superhard Fe-Ni based alloy wear-resistant coating of equiax crystal and preparation method thereof |
| US20220102737A1 (en) * | 2020-09-28 | 2022-03-31 | Hyzon Motors Inc. | Enhanced durability of fuel cell metallic bipolar plate |
| CN114023986A (en) * | 2021-09-28 | 2022-02-08 | 上海治臻新能源股份有限公司 | Composite coating for fuel cell titanium substrate bipolar plate and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116140613A (en) * | 2023-02-07 | 2023-05-23 | 深圳市氢蓝时代动力科技有限公司 | Corrosion-resistant conductive coating material for metal bipolar plate and preparation method thereof |
| CN116140613B (en) * | 2023-02-07 | 2023-11-24 | 深圳市氢蓝时代动力科技有限公司 | Corrosion-resistant conductive coating material for metal bipolar plate and preparation method thereof |
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