CN110783595B - Metal bipolar plate, preparation method thereof and fuel cell - Google Patents

Metal bipolar plate, preparation method thereof and fuel cell Download PDF

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CN110783595B
CN110783595B CN201910962316.1A CN201910962316A CN110783595B CN 110783595 B CN110783595 B CN 110783595B CN 201910962316 A CN201910962316 A CN 201910962316A CN 110783595 B CN110783595 B CN 110783595B
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metal oxide
metal
bipolar plate
metal substrate
coating
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CN110783595A (en
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上官鹏鹏
王海峰
王利生
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Fengyuan Xinchuang Technology Beijing Co ltd
Zhejiang Fengyuan Hydrogen Energy Technology Co ltd
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Fengyuan Xinchuang Technology Beijing Co ltd
Zhejiang Fengyuan Hydrogen Energy Technology Co ltd
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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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention relates to a metal bipolar plate, a preparation method thereof and a fuel cell, and relates to the technical field of fuel cells. The main technical scheme adopted is as follows: the metal bipolar plate comprises a metal substrate, a metal oxide coating and a conductive coating; wherein the metal oxide coating is deposited on the metal substrate and the metal oxide coating comprises an unsaturated metal oxide layer. A conductive coating is deposited on the metal oxide coating. The invention is mainly used for improving the corrosion resistance, the conductivity and the coating bonding force of the metal bipolar plate, thereby prolonging the service life of the metal bipolar plate and the fuel cell.

Description

Metal bipolar plate, preparation method thereof and fuel cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to a metal bipolar plate, a preparation method thereof and a fuel cell.
Background
In the fuel cell industry (e.g., PEM hydrogen production by electrolysis and PEMFC fuel cells), bipolar plates are one of the important components of fuel cells. In the past, the main material of the bipolar plate is graphite, which is expensive, so that the cost of the bipolar plate material accounts for 25-35% of the cost of the whole battery; furthermore, graphite materials have the disadvantage of poor machinability. Since the metal material has the advantages of low price, good machinability, good toughness, good strength, etc., the bipolar plate made of the metal material is considered as an inevitable choice for fuel cells by those skilled in the art. The bipolar plate needs to have excellent conductivity and corrosion resistance; therefore, the preparation of a corrosion-resistant conductive layer on a metal substrate is of great significance.
In the prior art, a method for modifying a metal substrate is to deposit a coating with corrosion resistance and electrical conductivity on the surface of the metal substrate by using a physical vapor deposition method. However, the metal bipolar plate manufactured by the technology has at least the following technical problems:
(1) because the metal bipolar plate has a harsh operating environment, strict limitations are put on the conductivity and the corrosion resistance of the coating, and the currently selected coating material cannot have both excellent corrosion resistance and conductivity.
(2) The coating has a pinhole phenomenon in the longitudinal direction, and in the corrosive environment of the fuel cell, corrosive media enter the film layer through the pinholes to reach the metal matrix and corrode the matrix.
Disclosure of Invention
In view of the above, the present invention provides a metal bipolar plate, a method for manufacturing the same, and a fuel cell, and mainly aims to improve the electrical conductivity and the corrosion resistance of the metal bipolar plate.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a metallic bipolar plate, wherein the metallic bipolar plate includes:
a metal substrate;
a metal oxide coating deposited on the metal substrate;
wherein the metal oxide coating comprises an unsaturated metal oxide layer.
Preferably, the metal oxide coating further comprises a saturated metal oxide layer; wherein the saturated metal oxide layer is located between the unsaturated metal oxide layer and the metal substrate.
Preferably, the metal component in the metal oxide coating comprises one or two of titanium Ti, aluminum Al.
Preferably, the thickness of the metal oxide coating is 20-100 nm. The thickness of the unsaturated metal oxide layer is 20-50 nm.
The metallic bipolar plate further comprises a conductive coating deposited on the metal oxide coatingThe above step (1); preferably, the conductive coating is an amorphous carbon film; further preferably, SP in the amorphous carbon film2The mass fraction of the hybrid carbon is 60-90%; preferably, the thickness of the conductive coating is 50nm to 5 μm.
Preferably, the coating bonding force of the metal bipolar plate is 48-55N; and/or the contact resistance of the metal bipolar plate is 1.2-2.2m omega cm2(ii) a Preferably 1.2 to 1.6 m.OMEGA.cm2(ii) a And/or the corrosion potential of the metal bipolar plate is 302-345mV, preferably 329-345 mV; and/or the corrosion current of the metal bipolar plate is 3.0 x 10-7-8.5×10-7A/cm2。
On the other hand, the preparation method of the metal bipolar plate comprises the following steps:
pretreatment: pretreating a metal substrate;
depositing a metal oxide coating: depositing a metal oxide coating on a surface of the metal substrate, and causing the metal oxide coating to comprise an unsaturated metal oxide layer.
Preferably, the step of pre-treating comprises:
first pretreatment: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
and (3) second pretreatment: carrying out surface ion sputtering and etching activation treatment on the metal substrate; preferably, bias magnetic control multi-arc ion plating equipment is adopted to carry out surface ion sputtering and etching activation treatment on the metal substrate; preferably, the second pretreatment step includes: after the metal substrate was transferred into a vacuum chamber, the vacuum degree of the vacuum chamber was evacuated to 1X 10-3～5×10-3Pa; heating a metal substrate to 150-500 ℃; introducing inert gas or nitrogen into the vacuum chamber, and maintaining the air pressure of the vacuum chamber at 0.05-1 Pa; and carrying out surface ion sputtering and etching activation treatment on the metal substrate for 3-15 min under the bias voltage of-600V to-1500V.
The step of depositing a metal oxide coating comprises:
1) depositing a saturated metal oxide coating on the metal substrate;
2) carrying out hydrogen etching treatment on the saturated metal oxide coating to enable the part, far away from the metal substrate, on the saturated metal oxide coating to form an unsaturated metal oxide layer;
preferably, the step 1) includes: introducing 100-500 sccm of inert gas and 5-50 sccm of oxygen into the vacuum chamber, opening the metal multi-arc target, and depositing a saturated metal oxide coating on the surface of the metal substrate; further preferably, the metal multi-arc target is a titanium and/or aluminum multi-arc target; the temperature of the metal substrate is 150-500 ℃; further preferably, the step 1) is carried out in a bias magnetic control multi-arc ion plating device;
preferably, the step 2) includes: introducing 100-500 sccm of inert gas and 5-50 sccm of hydrogen into a vacuum chamber, and reducing the metal oxide coating under the bias voltage of-800 to-1600V and the sputtering current of 20-35A; further preferably, in the step 2), the temperature of the metal substrate is 150-500 ℃; the reduction treatment time is 30-300 s.
Preferably, the method for preparing the metallic bipolar plate further comprises the following steps:
depositing a conductive coating, depositing a conductive coating on the metal oxide coating; preferably, the step of depositing the conductive coating comprises: the vacuum degree of the vacuum chamber is pumped to 1.5X 10-3～3×10-3Pa, introducing 50-500 sccm inert gas or nitrogen, setting the bias voltage to be-100 to-1500V, setting the temperature of the metal substrate to be 150-500 ℃, and depositing a conductive coating on the metal oxide coating for 0.5-4 h; further preferably, the conductive coating is an amorphous carbon film; preferably, the step of depositing the conductive coating is performed in a biased magnetron multi-arc ion plating apparatus.
In still another aspect, an embodiment of the present invention further provides a fuel cell, where the fuel cell includes the metal bipolar plate described in any one of the above.
Compared with the prior art, the metal bipolar plate, the preparation method thereof and the fuel cell have the following beneficial effects:
according to the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention, the metal oxide coating is deposited on the metal substrate, and the metal oxide coating comprises the unsaturated metal oxide layer, because the saturated metal oxide has very good corrosion resistance and compactness, but the conductivity is poor, the saturated metal oxide is changed into the unsaturated metal oxide (namely, the metal oxide coating comprises the unsaturated metal oxide layer (oxygen defect layer)) by reducing the oxygen partial pressure or performing a reduction method (namely, the etching effect of hydrogen) on the prepared saturated metal oxide in a hydrogen plasma atmosphere, so that the conductivity is greatly improved on the basis of not influencing the corrosion resistance, and the conductivity is equivalent to that of the metal layer. Therefore, the metal bipolar plate provided or prepared by the embodiment of the invention has excellent corrosion resistance and electrical conductivity.
Furthermore, the metal component of the metal bipolar plate provided by the embodiment of the invention is titanium and/or aluminum, and the titanium oxide or aluminum oxide film is a dense protective film naturally formed on the surface of the metal substrate, so that the metal bipolar plate is low in price, simple in preparation method, and very good in protection effect on a substrate, but very poor in conductivity. The inventor of the invention researches and finds that the unsaturated oxide of titanium and/or aluminum has excellent conductivity (the conductivity can be compared with metal), the corrosion resistance of the unsaturated oxide of titanium and/or aluminum is equivalent to that of a saturated oxide film of titanium and/or aluminum, the unsaturated oxide of titanium and/or aluminum is very compact, and the unsaturated oxide of titanium and/or aluminum also has very good matching property and bonding force with metal substrate materials and other coatings.
Furthermore, due to the compactness of the metal oxide, the coating has the minimum pinhole defect in the longitudinal direction, and the matrix material is effectively protected; meanwhile, the coated bipolar plate can be inevitably contacted with oxygen in the use process, and because the metal oxide coating in the application has oxygen unsaturation, the coating material can further absorb oxygen, the volume expands, the corrosion formed by hydrogen ions is repaired, and the service life of the metal bipolar plate is prolonged.
Further, in order to further improve the corrosion resistance and the electrical conductivity of the material, a multilayer protection method is adopted, and a layer of amorphous carbon film coating with a graphite-like structure is deposited on the surface of the metal oxide coating by using a magnetron sputtering technology; the carbon coating with cheap, conductive and corrosion-resistant graphitized structure has the thickness of only hundreds of nanometers, but can reduce the surface contact resistance of the bipolar plate.
On the other hand, the fuel cell provided by the embodiment of the invention comprises the metal bipolar plate, so that the performance of the fuel cell is improved, the service life of the fuel cell is prolonged, and the cost of the fuel cell is also reduced.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a schematic structural diagram of a metal bipolar plate according to an embodiment of the present invention;
fig. 2 is a schematic diagram illustrating an etching principle of a saturated metal oxide by hydrogen ions according to an embodiment of the present invention.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, embodiments of the present invention provide a metallic bipolar plate, as shown in fig. 1, including: metal substrate 1, metal oxide coating 2. Wherein a metal oxide coating 2 is deposited on a metal substrate 1. Here, the metal oxide coating 2 includes an unsaturated metal oxide layer 22 (also referred to as an oxygen-deficient layer or a hydrogen-etched layer), and the composition of the unsaturated metal oxide layer 22 is mainly an unsaturated metal oxide.
Preferably, as shown in fig. 1, the metal oxide coating 2 further comprises a saturated metal oxide layer 21; wherein the saturated metal oxide layer 21 is located between the unsaturated metal oxide layer 22 and the metal substrate 1. The main component of the saturated metal oxide layer 21 is a saturated metal oxide.
Preferably, the metal component in the metal oxide coating 2 is one or both of titanium Ti and aluminum Al (e.g., the component of the saturated metal oxide layer includes TiO)2、Al2O3One or two of the unsaturated metal oxide layer and the component of the unsaturated metal oxide layer comprise one or two of TiO and AlO). The thickness of the metal oxide coating 2 is 20-100 nm.
Preferably, the metallic bipolar plate as shown in fig. 1 further comprises: a conductive coating 3; wherein the conductive coating 3 is deposited on the metal oxide coating 2. Preferably, the conductive coating 3 is an amorphous carbon film; further preferably, SP in the amorphous carbon film2The mass fraction of the hybrid carbon is 60-90%. Preferably, the thickness of the conductive coating 3 is 50nm to 5 μm.
In the structure of the metal bipolar plate, the titanium oxide or aluminum oxide film is a layer of compact protective film naturally formed on the surface of the metal substrate, the price is low, the preparation method is simple, the metal bipolar plate has good protective effect on the metal substrate, but the conductivity is very poor. Through research, when the stoichiometric ratio of the metal oxide is changed, an oxygen defect layer is formed by reducing the oxygen partial pressure or performing a reduction method on the prepared titanium oxide in a hydrogen plasma atmosphere, so that the conductivity of the metal oxide coating material is qualitatively changed, and the conductivity of the metal oxide coating material can be comparable to that of metal. Meanwhile, the corrosion resistance of the material is almost unchanged, and the prepared film material is very compact and has very good matching property and bonding force with a metal substrate and other coatings.
Furthermore, due to the compactness of the metal oxide, the coating has the minimum pinhole defect in the longitudinal direction, and the metal substrate is effectively protected. Meanwhile, the metal bipolar plate is inevitably contacted with oxygen in the use process, and due to the unsaturation of the oxygen in the oxygen defect layer, the coating material can further absorb the oxygen, the volume expands, and the corrosion formed by hydrogen ions is repaired, so that the service life of the metal bipolar plate is prolonged.
And finally, in order to further improve the corrosion resistance and the electric conductivity of the metal bipolar plate, a multi-layer protection method is adopted, and a carbon film coating with a graphite-like structure is deposited on the surface of the metal oxide coating by using a magnetron sputtering technology. The carbon coating with cheap, conductive and corrosion-resistant graphitized structure has the thickness of only hundreds of nanometers, but can reduce the surface contact resistance of the bipolar plate to 1m omega/cm2The following.
On the other hand, the embodiment of the invention also provides a preparation method of the metal bipolar plate, which comprises the following steps:
1. pretreatment: the metal substrate is pretreated to improve the cleanliness and the surface roughness of the metal substrate. The method specifically comprises the following steps:
11) the first step of pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. And then, grinding by adopting alumina or diamond polishing paste to reduce texture defects formed in the molding of the bipolar plate. And after the polishing treatment is finished, cleaning the metal substrate by using pure water, putting the cleaned metal substrate into the pure water for storage, and blowing the metal substrate by using clean nitrogen before use.
The step is to improve the cleanness and the roughness of the metal substrate and increase the specific surface area of the metal substrate, so that the bonding force between the metal substrate and the coating is enhanced.
12) The second step of pretreatment: and carrying out ion sputtering on the metal substrate in a vacuum state. Specifically, a bias magnetic control multi-arc ion plating device is adopted, a clamp provided with a metal substrate is arranged in a vacuum chamber, and the vacuum chamber is vacuumized to 3 multiplied by 10-3Pa～6×10-3Pa, preferably 5X 10-5Pa, heating the metal substrate to 150-500 deg.C, introducing 0.5-1.5 Pa, preferably 1Pa inert gas such as argon, and biasingSetting the temperature to be-600V to-1500V, and carrying out surface ion sputtering and etching activation for 3-15 min.
Here, the purpose of the pretreatment operation by ion sputtering is to: in order to further remove the oxide on the surface of the metal substrate; meanwhile, the roughness of the surface of the metal substrate can be further improved through ion sputtering and etching activation, the surface area is increased, and the binding force between the metal substrate and the coating is enhanced.
2. Depositing a metal oxide coating: depositing a metal oxide coating on the surface of the metal substrate, and making the metal oxide coating comprise an oxygen defect layer. The method specifically comprises the following steps:
21) setting the flow of argon or other inert gases to be 100-500 sccm, and opening the argon or other inert gas control valve. Setting the flow rate of oxygen to be 5-50 sccm, and opening an oxygen control valve. Controlling the pressure of the vacuum chamber to be 0.1-0.5 Pa, heating the metal substrate to 150-500 ℃, and setting the bias voltage to-50V-700V. Turning on a multi-arc titanium target power supply, and setting the current value to be 10-150A; and/or turning on a multi-arc aluminum target power supply, and setting the current value to be 10-150A. The deposition time is 30 s-10 min.
22) Controlling the temperature of the metal substrate, introducing argon or other inert gases and hydrogen, setting negative bias of-800 to-1600V, and setting 20-35A sputtering current to perform reduction treatment on the metal oxide coating; preferably, the temperature of the metal substrate is 150-500 ℃; preferably, the flow rate of the argon or other inert gases is 100-500 sccm, the flow rate of the hydrogen is 5-50 sccm, and the vacuum degree is 0.1-0.5 Pa; preferably, the reduction treatment time is between 30 and 300 seconds.
Here, the principle of etching or reducing the saturated metal oxide by hydrogen ions is schematically shown in fig. 2. As shown in fig. 2, the saturated titanium and aluminum oxides are changed into unsaturated oxides by the etching reduction of hydrogen (hydrogen ions combine with oxygen in the saturated oxides to form water molecules); that is, one surface of the metal substrate having the saturated metal oxide coating layer is reduced to an unsaturated metal oxide layer.
3. And (3) depositing a conductive coating: a conductive coating is deposited over the corrosion-resistant coating.
The step of depositing a conductive coating comprises: the vacuum degree of the vacuum chamber is pumped to 1.5X 10-3～3×10-3Pa, introducing 50-500 sccm inert gas or nitrogen, setting the bias voltage to-100-1500V, starting a magnetron graphite target sputtering power supply, and setting the current to 10-50A; the temperature of the metal substrate is 150-500 ℃, and the conductive coating is deposited on the metal oxide coating for 0.5-4 h; further preferably, the conductive coating is an amorphous carbon film.
Example 1
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
first pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
And (3) second pretreatment: adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing argon gas of about 1Pa, and setting the bias voltage to-800V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
Depositing a saturated metal oxide coating: setting the flow of argon gas to be 300sccm, and opening an argon gas control valve; the oxygen flow rate was set to 10sccm, and the oxygen control valve was opened. The pressure in the vacuum chamber was controlled to 0.1Pa, the metal substrate was heated to 180 ℃ and the bias voltage was set at-200V. Turning on a multi-arc titanium target power supply, and setting the current value to be 50A; and depositing a titanium oxide coating on the metal substrate for 10 min.
Carrying out hydrogen etching treatment on the saturated metal oxide coating: controlling the temperature of the substrate to be 180 ℃, introducing 200sccm argon and 50sccm hydrogen, and controlling the vacuum degree to be 0.2 Pa; setting the sputtering current to be 30A, setting negative bias of-200V, and carrying out hydrogen etching treatment on the metal substrate; the hydrogen etching treatment time is 5 min.
Depositing an amorphous carbon film: closing a hydrogen valve, opening an argon valve, wherein the introduction amount of argon is 300sccm, maintaining the air pressure in a vacuum chamber at 0.2Pa, opening a multi-arc graphite target power supply, adjusting the current to 10A, keeping a workpiece bias power supply in a working state, controlling the bias equipment to be-380V, and controlling the temperature of a metal substrate at 200 ℃; an amorphous carbon film was deposited on the hydrogen-etched layer (oxygen-deficient layer) for 180 min.
Example 2
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
first pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
And (3) second pretreatment: adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing argon gas of about 1Pa, and setting the bias voltage to-800V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
Depositing a saturated metal oxide coating: setting the flow of argon gas to be 300sccm, and opening an argon gas control valve; the oxygen flow rate was set to 10sccm, and the oxygen control valve was opened. The pressure in the vacuum chamber was controlled to 0.5Pa, the metal substrate was heated to 180 ℃ and the bias voltage was set at-200V. Turning on a multi-arc titanium target power supply, and setting the current value to be 80A; and depositing a titanium oxide coating on the metal substrate for 10 min.
Carrying out hydrogen etching treatment on the saturated metal oxide coating: controlling the temperature of the substrate to be 180 ℃, introducing 100sccm argon and 50sccm hydrogen, and controlling the vacuum degree to be 0.2 Pa; setting the sputtering current to be 30A, setting negative bias of-200V, and carrying out hydrogen etching treatment on the metal substrate; the hydrogen etching treatment time is 5 min.
Depositing an amorphous carbon film: closing a hydrogen valve, opening an argon valve, wherein the introduction amount of argon is 300sccm, maintaining the air pressure in a vacuum chamber at 0.2Pa, opening a multi-arc graphite target power supply, adjusting the current to 10A, keeping a workpiece bias power supply in a working state, controlling the bias equipment to be-380V, and controlling the temperature of a metal substrate at 200 ℃; an amorphous carbon film was deposited on the hydrogen-etched layer (oxygen-deficient layer) for 180 min.
Example 3
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
first pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
And (3) second pretreatment: adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree to 5 multiplied by 10-3Pa, and heating the metal substrate to 180 DEGArgon gas with about 1Pa is introduced, and bias voltage is set to be-800V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
Depositing a saturated metal oxide coating: setting the flow of argon gas to be 300sccm, and opening an argon gas control valve; the oxygen flow rate was set to 10sccm, and the oxygen control valve was opened. The pressure in the vacuum chamber was controlled to 0.1Pa, the metal substrate was heated to 180 ℃ and the bias voltage was set at-200V. Turning on a multi-arc titanium target power supply, and setting the current value to be 50A; and depositing a titanium oxide coating on the metal substrate for 10 min.
Carrying out hydrogen etching treatment on the saturated metal oxide coating: controlling the temperature of the substrate to be 180 ℃, introducing 100sccm argon and 30sccm hydrogen, and controlling the vacuum degree to be 0.2 Pa; setting the sputtering current to be 30A, setting negative bias of-200V, and carrying out hydrogen etching treatment on the metal substrate; the hydrogen etching treatment time is 5 min.
Depositing an amorphous carbon film: closing a hydrogen valve, opening an argon valve, wherein the introduction amount of argon is 300sccm, maintaining the air pressure in a vacuum chamber at 0.2Pa, opening a multi-arc graphite target power supply, adjusting the current to 10A, keeping a workpiece bias power supply in a working state, controlling the bias equipment to be-380V, and controlling the temperature of a metal substrate at 200 ℃; an amorphous carbon film was deposited on the hydrogen-etched layer (oxygen-deficient layer) for 180 min.
Example 4
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
first pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
And (3) second pretreatment: adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing argon gas of about 1Pa, and setting the bias voltage to-800V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
Depositing a saturated metal oxide coating: setting the flow of argon gas to be 300sccm, and opening an argon gas control valve; the oxygen flow rate was set to 10sccm, and the oxygen control valve was opened. The pressure in the vacuum chamber was controlled to 0.4Pa, the metal substrate was heated to 180 ℃ and the bias voltage was set at-200V. Turning on a multi-arc titanium target power supply, and setting the current value to be 30A; and depositing a titanium oxide coating on the metal substrate for 10 min.
Carrying out hydrogen etching treatment on the saturated metal oxide coating: controlling the temperature of the substrate to be 180 ℃, introducing 100sccm argon and 50sccm hydrogen, and controlling the vacuum degree to be 0.2 Pa; setting the sputtering current to be 30A, setting negative bias of-300V, and carrying out hydrogen etching treatment on the metal substrate; the hydrogen etch process time was 200 seconds.
Depositing an amorphous carbon film: closing a hydrogen valve, opening an argon valve, wherein the introduction amount of argon is 300sccm, maintaining the air pressure in a vacuum chamber at 0.2Pa, opening a multi-arc graphite target power supply, adjusting the current to 10A, keeping a workpiece bias power supply in a working state, controlling the bias equipment to be-380V, and controlling the temperature of a metal substrate at 200 ℃; an amorphous carbon film was deposited on the hydrogen-etched layer (oxygen-deficient layer) for 180 min.
Example 5
In this example, a titanium plate was selected as the metal substrate. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
first pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
And (3) second pretreatment: adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing argon gas of about 1Pa, and setting the bias voltage to-800V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
Depositing a saturated metal oxide coating: setting the flow of argon gas to be 300sccm, and opening an argon gas control valve; the oxygen flow rate was set to 10sccm, and the oxygen control valve was opened. The pressure in the vacuum chamber was controlled to 0.1Pa, the metal substrate was heated to 180 ℃ and the bias voltage was set at-200V. Turning on a multi-arc titanium target power supply, and setting the current value to be 50A; and depositing a titanium oxide coating on the metal substrate for 10 min.
Carrying out hydrogen etching treatment on the saturated metal oxide coating: controlling the temperature of the substrate to be 180 ℃, introducing 200sccm argon and 50sccm hydrogen, and controlling the vacuum degree to be 0.2 Pa; setting the sputtering current to be 30A, setting negative bias of-200V, and carrying out hydrogen etching treatment on the metal substrate; the hydrogen etching treatment time is 5 min.
Depositing an amorphous carbon film: closing a hydrogen valve, opening an argon valve, wherein the introduction amount of argon is 300sccm, maintaining the air pressure in a vacuum chamber at 0.2Pa, opening a multi-arc graphite target power supply, adjusting the current to 10A, keeping a workpiece bias power supply in a working state, controlling the bias equipment to be-380V, and controlling the temperature of a metal substrate at 200 ℃; an amorphous carbon film was deposited on the hydrogen-etched layer (oxygen-deficient layer) for 180 min.
Example 6
This example differs from example 1 in that: in the step of depositing the saturated metal oxide coating, a power supply of a multi-arc titanium target is not turned on, and a multi-arc aluminum target is turned on, namely, an aluminum oxide coating is deposited on the metal substrate.
And other steps are consistent.
Example 7
This example differs from example 1 in that: in the step of depositing the saturated metal oxide coating, not only the multi-arc titanium target power supply is turned on, but also the multi-arc aluminum target, that is, the mixed coating of aluminum oxide and titanium oxide is deposited on the metal substrate.
And other steps are consistent.
The metal bipolar plate samples prepared in examples 1-7 were tested for performance and the results are shown in the table.
Table 1 shows the data of the performance test of the metal bipolar plates prepared in examples 1 to 7
Figure BDA0002229345600000131
As can be seen from the data in table 1, the metal bipolar plate prepared by the embodiment of the present invention has excellent conductivity and corrosion resistance, and the coating bonding force is high.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (18)

1. A metallic bipolar plate, comprising:
a metal substrate;
a metal oxide coating deposited on the metal substrate;
wherein the metal oxide coating comprises an unsaturated metal oxide layer and a saturated metal oxide layer; wherein the saturated metal oxide layer is located between the unsaturated metal oxide layer and the metal substrate;
and carrying out hydrogen etching treatment on the saturated metal oxide coating to form an unsaturated metal oxide layer on the part of the saturated metal oxide coating far away from the metal substrate.
2. The metallic bipolar plate of claim 1 wherein the metallic component of said metal oxide coating comprises one or both of titanium Ti, aluminum Al; and/or
The thickness of the metal oxide coating is 20-100 nm; and/or
The thickness of the unsaturated metal oxide layer is 20-50 nm.
3. Metallic bipolar plate according to claim 1 or 2, further comprising an electrically conductive coating deposited on the metal oxide coating.
4. Metallic bipolar plate as in claim 3,
the conductive coating is an amorphous carbon film.
5. Metallic bipolar plate as in claim 4,
SP in the amorphous carbon film2The mass fraction of the hybrid carbon is 60-90%.
6. Metallic bipolar plate as in claim 3,
the thickness of the conductive coating is 50 nm-5 mu m.
7. Metallic bipolar plate as in any of claims 1 to 2 and 4 to 6,
the coating bonding force of the metal bipolar plate is 48-55N; and/or
The contact resistance of the metal bipolar plate is 1.2-2.2m omega cm2(ii) a And/or
The corrosion potential of the metal bipolar plate is 302-345 mV; and/or
The corrosion current of the metal bipolar plate is 3.0 multiplied by 10-7-8.5×10-7 A/cm2。
8. The method of manufacturing a metallic bipolar plate as set forth in any one of claims 1 to 7, comprising the steps of:
pretreatment: pretreating a metal substrate;
depositing a metal oxide coating: depositing a metal oxide coating on the surface of the metal substrate, wherein the metal oxide coating comprises an unsaturated metal oxide layer;
the step of depositing a metal oxide coating comprises:
1) depositing a saturated metal oxide coating on the metal substrate;
2) and carrying out hydrogen etching treatment on the saturated metal oxide coating to enable the part, far away from the metal substrate, of the saturated metal oxide coating to form an unsaturated metal oxide layer.
9. The method of manufacturing a metallic bipolar plate as claimed in claim 8, wherein the step of pretreating comprises:
first pretreatment: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
and (3) second pretreatment: and carrying out surface ion sputtering and etching activation treatment on the metal substrate.
10. The method of manufacturing a metallic bipolar plate as claimed in claim 9,
performing surface ion sputtering and etching activation treatment on the metal substrate by adopting bias magnetic control multi-arc ion coating equipment; and/or
The second pretreatment step comprises: after the metal substrate was transferred into a vacuum chamber, the vacuum degree of the vacuum chamber was evacuated to 1X 10-3~5×10-3Pa; heating a metal substrate to 150-500 ℃;
introducing inert gas or nitrogen into the vacuum chamber, and maintaining the air pressure of the vacuum chamber at 0.05-1 Pa; and carrying out surface ion sputtering and etching activation treatment on the metal substrate for 3-15 min under the bias voltage of-600V to-1500V.
11. The method of claim 8, wherein the step 1) of depositing the metal oxide coating comprises: and introducing 100-500 sccm inert gas and 5-50 sccm oxygen into the vacuum chamber, opening the metal multi-arc target, and depositing a saturated metal oxide coating on the surface of the metal substrate.
12. The method of manufacturing a metallic bipolar plate as claimed in claim 11, wherein the metallic multi-arc target is a titanium and/or aluminum multi-arc target; and/or
The temperature of the metal substrate is 150-500 ℃; and/or
The step 1) is carried out in bias magnetic control multi-arc ion plating equipment.
13. The method of manufacturing a metallic bipolar plate as claimed in claim 8,
the step 2) of depositing the metal oxide coating comprises: and introducing 100-500 sccm of inert gas and 5-50 sccm of hydrogen into the vacuum chamber, and reducing the metal oxide coating under the bias voltage of-800-1600V and the sputtering current of 20-35A.
14. The method of manufacturing a metallic bipolar plate as claimed in claim 13,
in the step 2), the temperature of the metal substrate is 150-500 ℃; the reduction treatment time is 30-300 s.
15. The method of manufacturing a metallic bipolar plate as claimed in any one of claims 8 to 14, further comprising the steps of:
depositing a conductive coating, and depositing a conductive coating on the metal oxide coating.
16. The method of manufacturing a metallic bipolar plate as claimed in claim 15,
the step of depositing a conductive coating comprises: the vacuum degree of the vacuum chamber is pumped to 1.5X 10-3~3×10-3Pa, introducing 50-500 sccm inert gas or nitrogen, setting the bias voltage to be-100-1500V, setting the temperature of the metal substrate to be 150-500 ℃, and depositing the conductive coating on the metal oxide coating for 0.5-4 h.
17. The method of manufacturing a metallic bipolar plate as claimed in claim 16,
the conductive coating is an amorphous carbon film; and/or
The step of depositing the conductive coating is performed in a bias magnetic control multi-arc ion plating device.
18. A fuel cell comprising the metallic bipolar plate of any one of claims 1 to 7.
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