CN115411285A - Fuel cell bipolar plate containing anticorrosive film and preparation method thereof - Google Patents

Fuel cell bipolar plate containing anticorrosive film and preparation method thereof Download PDF

Info

Publication number
CN115411285A
CN115411285A CN202211226264.XA CN202211226264A CN115411285A CN 115411285 A CN115411285 A CN 115411285A CN 202211226264 A CN202211226264 A CN 202211226264A CN 115411285 A CN115411285 A CN 115411285A
Authority
CN
China
Prior art keywords
titanium
niobium
layer
bipolar plate
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211226264.XA
Other languages
Chinese (zh)
Inventor
孙德恩
陈君益
郑佳
李凤吉
李冠男
王姝
黄月华
张善勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest University
Original Assignee
Southwest University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest University filed Critical Southwest University
Priority to CN202211226264.XA priority Critical patent/CN115411285A/en
Publication of CN115411285A publication Critical patent/CN115411285A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

A fuel cell bipolar plate containing an anticorrosive film and a preparation method thereof. The invention provides a metal titanium bipolar plate, which comprises a titanium substrate and a film compounded on the titanium substrate; the film includes: a titanium bottom layer compounded on the titanium substrate; the niobium-titanium alloy transition layer is compounded on the titanium layer; and the niobium nitride layer is compounded on the niobium-titanium alloy transition layer. The invention particularly designs a metal titanium bipolar plate of a fuel cell, which comprises an anticorrosive coating with a specific structure and a specific composition. The surface coating of the bipolar plate of the fuel cell provided by the invention has fine grains, and the corrosion resistance performance under the working environment of the fuel cell is excellent; the surface film of the bipolar plate of the fuel cell is uniform and compact, the combination of the film and the matrix is good, and the film is not easy to fall off; meanwhile, the preparation method provided by the invention solves the problems of conductivity, corrosion resistance and binding force of the film and the matrix material, and the prepared coating has compact surface and section appearance and convenient and fast process.

Description

Fuel cell bipolar plate containing anticorrosive film and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cell bipolar plates, relates to a metal titanium bipolar plate, a preparation method and application thereof, and particularly relates to a fuel cell bipolar plate containing an anti-corrosion film and a preparation method thereof.
Background
A fuel cell is a device that directly converts chemical energy of fuel and oxidant into electrical energy under the action of a catalyst. The device is not limited by Carnot cycle, has the advantages of high energy conversion efficiency, high operation reliability, environmental protection, low noise and the like, and is considered to be a green energy conversion device which can replace the most promising traditional fossil energy. Among them, a Proton Exchange Membrane Fuel Cell (PEMFC) is used as a fifth generation fuel cell, and has the advantages of low working temperature, fast starting speed, high power density, and the like, and is considered as one of the most promising new clean energy sources.
The bipolar plate is one of the main components of the fuel cell, the mass accounts for about 60-80% of the whole fuel cell, and the cost accounts for 20-30%. It serves to separate the cathode from the anode, distribute oxygen and hydrogen required for the reaction of the cathode and the anode, collect current, conduct current, thermally manage the fuel cell through the flow field on the bipolar plate, support the membrane electrode, and most importantly, it can connect a plurality of single cells in series to form a complete cell stack. At present, the bipolar plate mainly comprises three types, namely a metal bipolar plate, a graphite bipolar plate and a composite material bipolar plate. Graphite bipolar plates are generally prepared by high-temperature treatment, the graphitization temperature is usually higher than 2500 ℃, and the process needs to be carried out under a strict temperature rise program and takes a long time. In addition, graphitization causes leakage inside the PEMFC due to evaporation of impurities, new pores occur, and the reaction gas concentration is reduced, thereby degrading the performance of the cell and the core. And the mechanical properties are inferior compared to other types of bipolar plates. Breakage easily occurs during the manufacturing process. The composite bipolar plate can better combine the advantages of the graphite plate and the metal plate, and has the characteristics of low density, corrosion resistance and easy forming. However, the current processing cycle is long, and the application is limited due to poor reliability in long-term operation. Metal bipolar plates have received much attention from the scientific community because of their good mechanical properties, high thermal and electrical conductivity, wide variety of materials, and the ability to form ultra-thin metal plates. However, they are susceptible to corrosion in the acidic environment of the PEMFC, and the dissolved ions poison the proton exchange membrane and catalyst, reducing the power output of the fuel cell.
Therefore, how to improve the corrosion resistance and the electrical conductivity of the metal bipolar plate is a major research hotspot at present, and is one of the problems to be solved urgently by many researchers in the industry.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a metallic titanium bipolar plate, a method for preparing the same, and applications thereof, in particular to a metal titanium bipolar plate containing NbN with a specific structure x The fuel cell bipolar plate of the anticorrosive film. The fuel cell bipolar plate provided by the invention is compounded with the specific anti-corrosion film, has better anti-corrosion performance and is not easy to fall off.
The invention provides a metal titanium bipolar plate, which comprises a titanium substrate and a film compounded on the titanium substrate;
the film includes: a titanium bottom layer compounded on the titanium substrate;
the niobium-titanium alloy transition layer is compounded on the titanium layer;
and the niobium nitride layer is compounded on the niobium-titanium alloy transition layer.
Preferably, the film is an anticorrosive film;
the thickness of the film is less than or equal to 600nm.
Preferably, in the film, the total mass content of niobium and titanium is 60-90%;
in the film, the mass content of nitrogen is 10-40%.
Preferably, the thickness of the titanium bottom layer is 10-50 nm;
the thickness of the niobium-titanium alloy transition layer is 20-100 nm;
the metallic titanium bipolar plate comprises a fuel cell bipolar plate.
Preferably, the niobium-titanium alloy transition layer comprises an alloy transition layer with gradient changes of niobium and titanium contents;
in the direction from the titanium bottom layer to the niobium nitride layer, the niobium-titanium alloy of the niobium-titanium alloy transition layer has increased niobium content and reduced titanium content;
the niobium-titanium alloy transition layer is provided with a niobium layer at one side close to the niobium nitride layer.
Preferably, the niobium content is increased, specifically, the niobium content is increased in a step-like gradient manner;
the niobium content is increased by increasing the sputtering power of niobium when preparing the niobium-titanium alloy transition layer;
the titanium content is reduced in a step-shaped gradient manner;
the reduction of the titanium content is realized by reducing the sputtering power of niobium when preparing the niobium-titanium alloy transition layer;
the thickness of the niobium layer is 20-60 nm.
The invention provides a preparation method of a metal titanium bipolar plate, which comprises the following steps:
1) Removing the surface oxide layer of the metal substrate to obtain a titanium substrate;
2) And performing magnetron sputtering coating on the titanium substrate obtained in the step to form a titanium layer on the surface of the titanium substrate, continuing to perform magnetron sputtering coating to form a niobium-titanium alloy layer, performing magnetron sputtering coating again to form a niobium nitride layer, and obtaining the metal titanium bipolar plate.
Preferably, the metal substrate is a pretreated metal substrate;
the pretreatment comprises polishing and/or ultrasonic cleaning;
the method for removing the surface oxidation layer comprises glow plasma cleaning;
the time for removing the surface oxidation layer is 30-60 minutes.
Preferably, the continuous magnetron sputtering coating is specifically carried out by adopting the trend of increasing the power of the niobium target and decreasing the power of the titanium target to carry out magnetron sputtering coating to form a niobium-titanium alloy layer;
the power increasing range of the niobium target is 100-400W;
the decreasing range of the power of the titanium target material is 300W-0.
The invention also provides application of the metal titanium bipolar plate in any one of the technical schemes or the metal titanium bipolar plate prepared by the preparation method in any one of the technical schemes in a fuel cell.
The invention provides a metal titanium bipolar plate, which comprises a titanium substrate and a film compounded on the titanium substrate; the film includes: a titanium bottom layer compounded on the titanium substrate; the niobium-titanium alloy transition layer is compounded on the titanium layer; and the niobium nitride layer is compounded on the niobium-titanium alloy transition layer. Compared with the prior art, the invention aims at the problems of the existing fuel cell metal bipolar plate in corrosion resistance, although stainless steel, titanium alloy and metal matrix composite material are applied to the manufacture of the bipolar plate, the defect of easy corrosion exists in the use process, and the research of the invention considers that the mode of modifying the surface coating is a suitable research direction. Based on the technical scheme, the invention particularly designs a metal titanium bipolar plate of a fuel cell, which comprises an anticorrosive coating with a specific structure and composition. Although titanium has the advantages of corrosion resistance, good conductivity, good processability and the like, and can reduce the cost of the fuel cell, titanium is easy to oxidize to form a non-conductive oxide layer. The invention carries out modification treatment on the surface of the metallic titanium and carries out physical vapor deposition of a niobium-titanium alloy layer on the surface of the metallic titanium, thus leading the transition layer and the base material to be tightly combined. And a niobium nitride layer is continuously deposited on the transition layer, and the coating is a ceramic layer, but has good conductivity and corrosion resistance, so that the contact resistance of the fuel cell interface can be effectively reduced, and the corrosion resistance of the fuel cell is improved. The temperature rise treatment is adopted in the magnetron sputtering coating process, so that the compactness of the appearance of the film is facilitated, and the performance of the film is improved.
The surface coating of the bipolar plate of the fuel cell provided by the invention has fine grains, and the corrosion resistance performance under the working environment of the fuel cell is excellent; the surface film of the fuel cell bipolar plate is uniform and compact, the combination of the film and the matrix is good, and the film is not easy to fall off; meanwhile, the preparation method provided by the invention solves the problems of conductivity, corrosion resistance and binding force of the film and the matrix material, and the prepared coating has compact surface and section appearance and convenient and fast process.
Experimental results show that the corrosion resistance and the conductivity of the surface-modified titanium bipolar plate prepared by the invention are greatly improved, and the surface coating has good stability, which indicates that the prepared surface coating greatly improves the performance of the titanium bipolar plate.
Drawings
FIG. 1 is a schematic view of the structure of an anticorrosive film provided by the present invention;
FIG. 2 shows the results of electrochemical testing of metal plates prepared according to the present invention in a fuel cell environment;
fig. 3 is a coating contact resistance test of the metal plate prepared by the invention in a fuel cell environment.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytical grade or purity conventional in the field of fuel cell bipolar plate production.
The invention provides a metal titanium bipolar plate, which comprises a titanium substrate and a film compounded on the titanium substrate;
the film includes: a titanium bottom layer compounded on the titanium substrate;
the niobium-titanium alloy transition layer is compounded on the titanium layer;
and the niobium nitride layer is compounded on the niobium-titanium alloy transition layer.
In the present invention, the film is preferably an anticorrosive film.
In the present invention, the thickness of the thin film is preferably 600nm or less, more preferably 500nm or less, and still more preferably 400nm or less.
In the present invention, the total mass content of niobium and titanium in the thin film is preferably 60 to 90%, more preferably 65 to 85%, and still more preferably 70 to 80%.
In the present invention, the nitrogen content in the thin film is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass.
In the present invention, the thickness of the titanium underlayer is preferably 10 to 50nm, more preferably 15 to 45nm, more preferably 20 to 40nm, and more preferably 25 to 35nm.
In the present invention, the thickness of the niobium-titanium alloy transition layer is preferably 20 to 100nm, more preferably 35 to 85nm, and still more preferably 50 to 70nm.
In the present invention, the metallic titanium bipolar plate preferably comprises a fuel cell bipolar plate.
In the present invention, the niobium-titanium alloy transition layer preferably comprises an alloy transition layer having a gradient of niobium and titanium content.
In the present invention, it is preferable that the niobium content in the niobium-titanium alloy of the niobium-titanium alloy transition layer increases and the titanium content decreases from the titanium underlayer to the niobium nitride layer.
In the present invention, the niobium-titanium alloy transition layer preferably has a niobium layer on the side close to the niobium nitride layer.
In the present invention, the increase in the niobium content is particularly preferably such that the niobium content increases in a stepwise gradient.
In the present invention, it is particularly preferable that the titanium content is decreased in a stepwise gradient.
In the present invention, the thickness of the niobium layer is preferably 20 to 60nm, more preferably 20 to 50nm, and still more preferably 25 to 40nm.
The invention is a complete and detailed integral technical scheme, which better improves the corrosion resistance of the fuel cell bipolar plate and the stability of the anticorrosive film, and ensures the conductivity of the fuel cell bipolar plate, and the fuel cell metal titanium bipolar plate containing the anticorrosive film can be specifically of the following structure:
the fuel cell bipolar plate comprises a metal substrate and a film coated on the surface of the substrate, wherein the film sequentially comprises a surface nitrogen-doped niobium nitride layer, a sputtering power gradient niobium-titanium alloy transition layer and a pure titanium priming layer, and the metal substrate is a titanium plate.
Wherein, in the whole composition of the film, the total content of the metal niobium and the titanium is 60 to 90 percent, and the nitrogen content is 10 to 40 percent.
Wherein the total thickness of the film is 400-600 nm, the thickness of the transition layer is about 20-100 nm, and the thickness of the bottom layer is 10-50 nm.
The invention provides a preparation method of a metal titanium bipolar plate, which comprises the following steps:
1) Removing the surface oxide layer of the metal substrate to obtain a titanium substrate;
2) And performing magnetron sputtering coating on the titanium substrate obtained in the step to form a titanium layer on the surface of the titanium substrate, continuing magnetron sputtering coating to form a niobium-titanium alloy layer, and performing magnetron sputtering coating again to form a niobium nitride layer to obtain the metal titanium bipolar plate.
The method comprises the steps of removing an oxide layer on the surface of a metal substrate to obtain a titanium substrate.
In the present invention, the metal substrate is preferably a pretreated metal substrate.
In the present invention, the pretreatment preferably includes polishing and/or ultrasonic cleaning, more preferably polishing or ultrasonic cleaning.
In the present invention, the means for removing the surface oxide layer preferably includes glow plasma cleaning.
In the present invention, the time for removing the surface oxide layer is preferably 30 to 60 minutes, more preferably 35 to 55 minutes, and still more preferably 40 to 50 minutes.
Finally, performing magnetron sputtering coating on the titanium substrate obtained in the step to form a titanium layer on the surface of the titanium substrate, continuing magnetron sputtering coating to form a niobium-titanium alloy layer, and performing magnetron sputtering coating again to form a niobium nitride layer to obtain the metal titanium bipolar plate.
In the present invention, the continuous magnetron sputtering coating is preferably performed by performing magnetron sputtering coating using a trend of increasing the niobium target power and decreasing the titanium target power to form a niobium-titanium alloy layer.
In the present invention, the range of increasing the niobium target power is preferably 100 to 400W, more preferably 150 to 350W, and still more preferably 200 to 300W.
In the present invention, the range in which the power of the titanium target decreases is preferably 300W to 0, more preferably 250W to 50, and still more preferably 200W to 100.
The invention is a complete and detailed integral technical scheme, which better improves the corrosion resistance of the fuel cell bipolar plate and the stability of the anticorrosive film, and ensures the conductivity of the fuel cell bipolar plate, and the preparation method of the fuel cell metal titanium bipolar plate containing the anticorrosive film preferably comprises the following steps:
the preparation method of the bipolar plate of the fuel cell provided by the invention comprises the following steps:
polishing and ultrasonically cleaning the metal substrate to remove rust and oil stains on the base material;
placing the pretreated metal substrate into a vacuum chamber for etching, and removing an oxide film on the surface of the substrate;
performing magnetron sputtering coating on the etched metal substrate to form a titanium layer;
continuously carrying out magnetron sputtering film coating on the sample subjected to magnetron sputtering to form a niobium-titanium alloy layer;
and continuously carrying out magnetron sputtering film coating on the sample subjected to magnetron sputtering to form the niobium nitride layer.
Wherein, the polishing treatment comprises the step of polishing the metal substrate by using sand paper of 400#, 600#, 800#, 1000 #.
Wherein, in the preparation process of the niobium-titanium alloy layer, two metal target materials are adopted for film plating in an increasing and decreasing way respectively.
Wherein, the workpiece to be plated is cleaned by ethanol and acetone in an ultrasonic way and dried by hot air (80-120 ℃) to remove stains such as rust, oil stain and the like on the workpiece.
Furthermore, the preparation steps of the fuel cell metal bipolar plate containing the film can specifically comprise the following steps:
firstly, grinding an oxidation film on the surface of a titanium sheet by using 400#, 600#, 800# and 1000# abrasive paper, and then carrying out ultrasonic cleaning on the titanium sheet by sequentially using alcohol and acetone to remove impurities and oil stains on the surface;
step two, putting the pretreated sample into a vacuum cavity; (ii) a The vacuum chamber is evacuated and simultaneously heated. Keeping the heating temperature at 250-300 ℃. When the vacuum degree of the vacuum chamber is lower than 5 multiplied by 10 -5 After the Torr, the vacuum chamber is regulated to be stabilized at 190-210 ℃, and the vacuum chamber is continuously pumped to 5 x 10 -6 Torr。
And step three, introducing argon into the vacuum chamber, simultaneously starting a bias voltage power supply, setting the bias voltage value to be-100V, and performing plasma glow cleaning on the sample to be plated for 30-60 minutes, wherein the bias voltage power supply is a radio frequency power supply.
Depositing a metal priming coat by adopting a magnetron sputtering method, wherein the thickness of the bonding layer is 0.005-0.03 micrometer, and the metal is a transition metal titanium element; in the deposition process, a bias power supply is set to be-50V, the bias power supply is a radio frequency power supply, and the sputtering power is 300W; depositing an alloy transition layer by adopting a magnetron sputtering method under the condition of reactive vapor deposition, wherein the thickness of the transition layer is 0.04-0.1 micron, and the metal is titanium element and niobium element; in the deposition process, the bias power supply is set to be 50V below zero, the bias power supply is a radio frequency power supply, the power of the titanium target shows a power decreasing trend from 300W to 0W, and the power of the niobium target shows a power increasing trend from 100W to 400W.
Step five, continuously depositing a layer of nitride film on the transition layer by adopting a magnetron sputtering method, wherein the flow of nitrogen is 6-12 sccm, the thickness of the film layer is 0.3-0.5 micron, and the metal is niobium; in the deposition process, the bias power supply is set at-50V, the bias power supply is a radio frequency power supply, and the power of the niobium target is 400W.
Referring to fig. 1, fig. 1 is a schematic view of the structure of the corrosion-resistant film provided by the present invention.
The key links of the invention are the treatment of the base material, the selection of the plating layer and the preparation process, which complement each other. The nitrogen atoms and the niobium atoms are deposited on the surface of the metallic titanium to form a niobium nitride film, and the film has stronger corrosion resistance. Because an oxide coating is easily formed on the surface of titanium, the binding force of the film is poor if magnetron sputtering coating is directly carried out on the titanium. The invention firstly polishes the titanium plate, removes the oxide layer, then prepares the base coat and the transition layer, respectively forms a layer of titanium film and a layer of niobium-titanium alloy film, so as to improve the film binding force, thereby effectively solving the problem of the bipolar plate in the practical application.
The invention provides application of the metal titanium bipolar plate in any one of the technical schemes or the metal titanium bipolar plate prepared by the preparation method in any one of the technical schemes in a fuel cell.
In particular, the NbN prepared by the invention has high corrosion resistance and conductivity x The titanium metal bipolar plate is applied to a proton exchange membrane fuel cell bipolar plate.
The invention provides a fuel cell bipolar plate containing an anticorrosive film and a preparation method thereof. The titanium metal has the advantages of corrosion resistance, good conductivity, good processing performance and the like, and can reduce the cost of the fuel cell, but the titanium is easy to oxidize to form a non-conductive oxide layer, so the invention particularly designs the metal titanium bipolar plate of the fuel cell, which contains the anti-corrosion coating with a specific structure and composition. The invention carries out modification treatment on the surface of the metal titanium and carries out physical vapor deposition of a niobium-titanium alloy layer on the surface of the metal titanium, thus leading the transition layer and the base material to be tightly combined. And the niobium nitride layer is continuously deposited on the transition layer, and the coating is a ceramic layer, but has good conductivity and corrosion resistance, so that the contact resistance of the interface of the fuel cell can be effectively reduced, and the corrosion resistance of the fuel cell is improved. The temperature rise treatment is adopted in the magnetron sputtering coating process, so that the compactness of the film appearance is facilitated, and the performance of the film is further improved.
The surface coating of the bipolar plate of the fuel cell provided by the invention has fine grains, and the corrosion resistance performance under the working environment of the fuel cell is excellent; the surface film of the fuel cell bipolar plate is uniform and compact, the combination of the film and the matrix is good, and the film is not easy to fall off; meanwhile, the preparation method provided by the invention solves the problems of conductivity, corrosion resistance and binding force of the film and the matrix material, and the prepared coating has compact surface and section appearance and convenient and fast process.
The key links of the invention are the treatment of the base material, the selection of the plating layer and the preparation process, which complement each other. The nitrogen atoms and the niobium atoms are deposited on the surface of the metallic titanium to form a niobium nitride film, and the film has stronger corrosion resistance. Because the titanium surface is easy to form an oxide coating, the film has poor binding force if the magnetron sputtering coating is directly carried out on the titanium surface. The invention firstly polishes the titanium plate, removes the oxide layer, then prepares the base coat and the transition layer, respectively forms a layer of titanium film and a layer of niobium-titanium alloy film, so as to improve the film binding force, thereby effectively solving the problem of the bipolar plate in the practical application.
Experimental results show that the corrosion resistance and the conductivity of the surface-modified titanium bipolar plate prepared by the invention are greatly improved, and the surface coating has good stability, which indicates that the prepared surface coating greatly improves the performance of the titanium bipolar plate.
In order to further illustrate the present invention, the following will describe in detail a metallic titanium bipolar plate and its manufacturing method and application in conjunction with the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed implementation and specific operation procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Pretreating a metal polar plate: and (3) grinding an oxidation film on the surface of the titanium sheet by using 400#, 600#, 800# and 1000# abrasive paper, and then carrying out ultrasonic cleaning on the titanium sheet by using alcohol and acetone in sequence to remove impurities and oil stains on the surface. The material is pretreated, so that the binding force of the coating can be improved, the quality of the coating can be improved, and otherwise, the coating can be uneven or fall off.
Preparing a surface coating: will be provided withThe titanium plate is placed in a vacuum chamber and pumped to the vacuum degree of 10 -6 After the Torr, magnetron sputtering coating is carried out. Controlling the bias voltage to be-50V, controlling the power of the titanium target to be 300W, and depositing a titanium base coat with the thickness of 10nm. Keeping the bias voltage unchanged, ensuring that the power of the titanium target shows the power decreasing trend of 300W-0W, ensuring that the power of the niobium target shows the power increasing trend of 100W-400W, and depositing a niobium-titanium alloy transition layer with the thickness of 50nm. And continuously keeping the bias voltage unchanged, wherein the niobium target power is 400W, the nitrogen flux is 12sccm, and a niobium nitride layer with the thickness of 350nm is deposited. After the coating was prepared, the resulting structure is shown in FIG. 1.
And (3) carrying out performance detection on the prepared metal pole plate with the coating.
Referring to fig. 2, fig. 2 shows the electrochemical test results of the metal plate prepared according to the present invention in a fuel cell environment.
As shown in fig. 2, the stabilized corrosion current density reached 10 -7 μA/cm 2 The corrosion performance requirement index of the 2020 United states department of energy for the fuel cell bipolar plate is reached.
Referring to fig. 3, fig. 3 is a coating contact resistance test of a metal plate prepared according to the present invention in a fuel cell environment.
As shown in FIG. 3, it can be seen that the contact resistance significantly decreases with increasing pressure, and is 1.125 m.OMEGA.. Cm at 1.4MPa 2 And the requirement index of 2020 United states department of energy for the conductivity of the fuel cell bipolar plate is also met.
Example 2
Pretreating a metal polar plate: and (3) grinding an oxidation film on the surface of the titanium sheet by using 400#, 600#, 800# and 1000# abrasive paper, and then carrying out ultrasonic cleaning on the titanium sheet by using alcohol and acetone in sequence to remove impurities and oil stains on the surface. The material is pretreated, so that the binding force of the coating can be improved, the quality of the coating can be improved, and otherwise, the coating can be uneven or fall off.
Preparing a surface coating: placing the titanium plate in a vacuum chamber and pumping to a vacuum degree of 10 -6 After the Torr, magnetron sputtering coating is carried out. Controlling the bias voltage to be-50V, controlling the power of the titanium target to be 300W, and depositing a titanium base coat with the thickness of 10nm. Keeping the bias voltage unchanged, and the power of the titanium target is 300W-0WThe power of the niobium target is increased gradually from 100W to 400W, and a niobium-titanium alloy transition layer is deposited with the thickness of 50nm. And continuously keeping the bias voltage unchanged, wherein the niobium target power is 400W, the nitrogen flux is 6sccm, and a niobium nitride layer with the thickness of 350nm is deposited.
And (3) carrying out performance detection on the prepared metal pole plate with the coating. The stabilized corrosion current density reaches 5.93 multiplied by 10 -7 μA/cm 2 And the corrosion performance requirement index of the United states energy department for the fuel cell bipolar plate in 2020 is reached. 3.752 m.OMEGA.. Cm under 1.4MPa 2 And the requirement index of the energy source department of the United states in 2020 on the conductivity of the bipolar plate of the fuel cell is also met.
Example 3
Pretreating a metal polar plate: and (3) grinding an oxidation film on the surface of the titanium sheet by using 400#, 600#, 800# and 1000# abrasive paper, and then carrying out ultrasonic cleaning on the titanium sheet by using alcohol and acetone in sequence to remove impurities and oil stains on the surface. The material is pretreated, so that the binding force of the coating can be improved, the quality of the coating can be improved, and otherwise, the coating can be uneven or fall off.
Preparing a surface coating: placing the titanium plate in a vacuum chamber and pumping to a vacuum degree of 10 -6 After the Torr, magnetron sputtering coating is carried out. Controlling the bias voltage to be-50V, controlling the power of the titanium target to be 300W, and depositing a titanium base coat with the thickness of 10nm. Keeping the bias voltage unchanged, ensuring that the power of the titanium target shows the power decreasing trend of 300W-0W, ensuring that the power of the niobium target shows the power increasing trend of 100W-400W, and depositing a niobium-titanium alloy transition layer with the thickness of 50nm. And continuously keeping the bias voltage unchanged, wherein the niobium target power is 400W, the nitrogen flux is 9sccm, and a niobium nitride layer with the thickness of 350nm is deposited.
And (4) carrying out performance detection on the prepared metal pole plate with the coating. The stabilized corrosion current density reaches 3.39 multiplied by 10 -7 μA/cm 2 The corrosion performance requirement index of the 2020 United states department of energy for the fuel cell bipolar plate is reached. At 1.4MPa, 2.375m omega cm 2 And the requirement index of the energy source department of the United states in 2020 on the conductivity of the bipolar plate of the fuel cell is also met.
The foregoing detailed description of the present invention provides a fuel cell bipolar plate with a corrosion resistant membrane and a method for making the same, which is described herein using specific examples to illustrate the principles and embodiments of the present invention, but which are presented solely to aid in the understanding of the methods and their underlying concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. A metal titanium bipolar plate is characterized by comprising a titanium substrate and a film compounded on the titanium substrate;
the film includes: a titanium bottom layer compounded on the titanium substrate;
the niobium-titanium alloy transition layer is compounded on the titanium layer;
and the niobium nitride layer is compounded on the niobium-titanium alloy transition layer.
2. The metallic titanium bipolar plate of claim 1, wherein said film is an anti-corrosive film;
the thickness of the film is less than or equal to 600nm.
3. The bipolar plate of claim 1, wherein the total mass content of niobium and titanium in said film is 60-90%;
in the film, the mass content of nitrogen is 10-40%.
4. The metallic titanium bipolar plate of claim 1, wherein said titanium underlayer has a thickness of 10 to 50nm;
the thickness of the niobium-titanium alloy transition layer is 20-100 nm;
the metallic titanium bipolar plate comprises a fuel cell bipolar plate.
5. The metallic titanium bipolar plate of claim 1, wherein said niobium-titanium alloy transition layer comprises an alloy transition layer having a gradient in niobium and titanium content;
in the direction from the titanium bottom layer to the niobium nitride layer, the niobium-titanium alloy of the niobium-titanium alloy transition layer has increased niobium content and reduced titanium content;
the niobium-titanium alloy transition layer is provided with a niobium layer at one side close to the niobium nitride layer.
6. The metallic titanium bipolar plate of claim 5, wherein said increase in niobium content is specifically a stepwise gradient increase in niobium content;
the niobium content is increased by increasing the sputtering power of niobium when preparing the niobium-titanium alloy transition layer;
the titanium content is reduced in a step-shaped gradient manner;
the reduction of the titanium content is realized by reducing the sputtering power of niobium when the niobium-titanium alloy transition layer is prepared;
the thickness of the niobium layer is 20-60 nm.
7. The preparation method of the metal titanium bipolar plate is characterized by comprising the following steps:
1) Removing the surface oxide layer of the metal substrate to obtain a titanium substrate;
2) And performing magnetron sputtering coating on the titanium substrate obtained in the step to form a titanium layer on the surface of the titanium substrate, continuing magnetron sputtering coating to form a niobium-titanium alloy layer, and performing magnetron sputtering coating again to form a niobium nitride layer to obtain the metal titanium bipolar plate.
8. The production method according to claim 7, wherein the metal substrate is a pretreated metal substrate;
the pretreatment comprises polishing and/or ultrasonic cleaning;
the method for removing the surface oxidation layer comprises glow plasma cleaning;
the time for removing the surface oxidation layer is 30-60 minutes.
9. The preparation method according to claim 8, wherein the continuous magnetron sputtering coating is specifically carried out by adopting a trend of increasing the niobium target power and decreasing the titanium target power to carry out magnetron sputtering coating to form a niobium-titanium alloy layer;
the power increasing range of the niobium target is 100-400W;
the decreasing range of the power of the titanium target material is 300W-0.
10. Use of the metallic titanium bipolar plate according to any one of claims 1 to 6 or the metallic titanium bipolar plate prepared by the preparation method according to any one of claims 7 to 9 in a fuel cell.
CN202211226264.XA 2022-10-09 2022-10-09 Fuel cell bipolar plate containing anticorrosive film and preparation method thereof Pending CN115411285A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211226264.XA CN115411285A (en) 2022-10-09 2022-10-09 Fuel cell bipolar plate containing anticorrosive film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211226264.XA CN115411285A (en) 2022-10-09 2022-10-09 Fuel cell bipolar plate containing anticorrosive film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115411285A true CN115411285A (en) 2022-11-29

Family

ID=84168389

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211226264.XA Pending CN115411285A (en) 2022-10-09 2022-10-09 Fuel cell bipolar plate containing anticorrosive film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115411285A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117626183A (en) * 2024-01-23 2024-03-01 北京科技大学 Conductive corrosion-resistant coating and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117626183A (en) * 2024-01-23 2024-03-01 北京科技大学 Conductive corrosion-resistant coating and preparation method and application thereof
CN117626183B (en) * 2024-01-23 2024-04-30 北京科技大学 Conductive corrosion-resistant coating and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN106374116B (en) High-entropy alloy composite coating and technique on a kind of fuel battery metal double polar plate
WO2021259046A1 (en) Method for preparing cr-al-c based max phase coating and use thereof
CN110684946B (en) Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof
CN109346743B (en) Conductive corrosion-resistant coating for metal bipolar plate of fuel cell
CN110137525A (en) A kind of fuel battery metal double polar plate coating and technology of preparing
CN101800318B (en) Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof
WO2023284596A1 (en) High-conductivity, corrosion-resistant and long-lifetime max phase solid solution composite coating, and preparation method therefor and use thereof
WO2023000913A1 (en) High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating, preparation method therefor, and application thereof
WO2023197469A1 (en) High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating, and preparation method therefor and use thereof
CN114665114A (en) Multilayer composite carbon coating and preparation method and application thereof
CN115411285A (en) Fuel cell bipolar plate containing anticorrosive film and preparation method thereof
CN112820890B (en) Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate
CN114976089A (en) Metal bipolar plate with coating and preparation method thereof
CN114231925A (en) Fuel cell metal bipolar plate composite coating and preparation method thereof
CN113025980A (en) Corrosion-resistant film layer for fuel cell bipolar plate and preparation method thereof
CN110970626B (en) Fuel cell bipolar plate and coating thereof
CN201717318U (en) Metal bipolar plate for proton exchange membrane fuel cell
CN112993293A (en) Metal bipolar plate of fuel cell and preparation method thereof
CN115928017A (en) High-conductivity corrosion-resistant protective composite coating and preparation method and application thereof
CN115029663A (en) Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell
CN112993299B (en) Silicon-doped niobium carbide coating of metal bipolar plate of fuel cell and preparation method thereof
CN112952129B (en) Metal bipolar plate with nano TaNbN modified layer and preparation method thereof
CN112111721B (en) Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate
CN115020734A (en) Fuel cell metal bipolar plate composite coating and preparation method thereof
CN112993276A (en) Metal bipolar plate for Nb-Cr-C coating modified fuel cell and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination