CN114214658A - Composite coating for water electrolysis metal bipolar plate and preparation method thereof - Google Patents
Composite coating for water electrolysis metal bipolar plate and preparation method thereof Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/036—Bipolar electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a composite coating for a water electrolysis metal bipolar plate and a preparation method thereof. The composite coating comprises a self-healing layer and an anti-corrosion layer which are alternately arranged along the surface of the metal bipolar plate to the outside in sequence, the self-healing layer and the anti-corrosion layer are at least alternated once, and the outermost layer is a conductive layer; the self-healing layer is one or more than two alloys of titanium, zirconium, niobium, chromium and tantalum, the compact corrosion-resistant layer is a transition metal oxynitride layer, and the outermost conductive layer is a transition metal nitride layer. The composite coating can keep higher conductivity and better structural integrity under the water electrolysis environment, reduce the contact resistance and corrosion current of the metal plate base material and improve the durability of the metal plate.
Description
Technical Field
The invention belongs to the field of water electrolysis, and particularly relates to a composite coating for a water electrolysis metal bipolar plate.
Background
Proton exchange membrane water electrolysis is considered to be an ideal alternative to alkaline water electrolysis, with its higher current density and operating power, and flexibility of dynamic operation, making them ideal for energy storage systems for intermittent energy sources (e.g., wind, solar, tidal, etc.). The membranes in the cells provide high proton conductivity, low gas permeability and ensure a compact system design, and no liquid alkaline electrolyte circulation, which makes proton exchange membrane cells safer and more reliable than alkaline cells. Bipolar plates are an important component of proton exchange membrane cells, primarily for separating the cell bodies, conducting heat and current between the cell bodies, and distributing reactants within the cell. The bipolar plate must have high corrosion resistance, high mechanical strength, high shock resistance, and be easy to mass produce. Titanium is now commonly used as a bipolar plate material in proton exchange membrane water electrolysers based on high anodic potentials during operation and acidic environment. However, the surface passivation of titanium can seriously affect the conductivity of the titanium, and further limit the working efficiency of the electrolytic cell, so that the surface modification of the titanium material to improve the corrosion-resistant conductivity of the titanium material is very important.
Disclosure of Invention
Aiming at the existing problems, the invention provides a water electrolysis metal bipolar plate surface modified composite coating with both conductive and corrosion resistant functions.
The technical scheme adopted by the invention is as follows:
a composite coating for a water electrolysis metal bipolar plate comprises a self-healing layer and an anti-corrosion layer which are alternately arranged along the surface of the metal bipolar plate to the outside in sequence, wherein the self-healing layer and the anti-corrosion layer are at least alternated once, and the outermost layer is a conductive layer;
the self-healing layer is one or more than two alloys of titanium, zirconium, niobium, chromium and tantalum;
the compact corrosion-resistant layer is a transition metal oxynitride layer, wherein the transition metal oxynitride comprises at least one of titanium oxynitride, zirconium oxynitride and niobium oxynitride, and the atomic proportion of oxygen atoms is 1-20%;
the conducting layer is a transition metal nitride layer, wherein the transition metal nitride comprises at least one of titanium nitride, zirconium nitride, niobium nitride, chromium nitride and niobium nitride.
In the above technical solution, further, in the transition metal oxynitride, the atomic ratio of oxygen atoms is 5% to 15%.
In the above technical solution, further, the thickness of the self-healing layer is 20-200nm, the thickness of the dense corrosion-resistant layer is 20-300nm, and the thickness of the conductive layer is 50-800 nm.
In the above technical solution, further, the thickness of the self-healing layer is 30-100nm, the thickness of the corrosion-resistant layer is 50-200nm, and the thickness of the conductive layer is 100-500 nm.
The preparation method of the composite coating comprises the following steps:
(1) pretreating the metal bipolar plate base material to remove surface stains and an oxide film;
(2) sequentially and alternately depositing a self-healing layer and an anti-corrosion layer on the surface of the pretreated metal bipolar plate base material; the preparation method of the self-healing layer comprises ion implantation, magnetron sputtering, multi-arc ion plating and plasma spraying; the preparation method of the compact corrosion-resistant layer comprises magnetron sputtering, multi-arc ion plating and atomic layer deposition; the preparation method of the conducting layer comprises magnetron sputtering, multi-arc ion plating and plasma spraying;
(3) depositing a conductive layer on the surface of the outermost corrosion-resistant layer deposited in the step (2); the preparation method of the conducting layer comprises at least one of magnetron sputtering, multi-arc ion plating and plasma spraying.
In the above technical solution, further, the step (1) includes the following steps: sequentially carrying out water washing and alcohol washing on the metal bipolar plate substrate to remove surface stains, and then cleaning and removing a surface oxidation film through magnetron sputtering; in the sputtering cleaning process, the pressure of the chamber is 0.3-1.0Pa, the applied voltage is-500V to-800V, and the cleaning time is 5-30 min.
In the above technical solution, further, in the step (2), the one-time alternation of the self-healing layer and the corrosion resistant layer includes the following steps: depositing a self-healing layer by a magnetron sputtering method, introducing nitrogen and oxygen as reaction gases after the deposition of the self-healing layer is finished, and depositing an anti-corrosion layer on the surface of the self-healing layer by magnetron sputtering;
wherein, in the deposition process of the self-healing layer, the pressure of the cavity is 0.3-1.0Pa, the applied current is 2-8A, and the deposition time is 3-30 min; in the process of depositing the corrosion-resistant layer, the flow rates of nitrogen and oxygen are respectively 10-30sccm and 2-10sccm, the pressure of the chamber is 0.3-1.0Pa, the applied current is 2-10A, and the deposition time is 10-40 min.
In the above technical solution, further, the step (3) includes the following steps: taking nitrogen as reaction gas, and depositing a conductive layer by magnetron sputtering; the flow rate of nitrogen is 10-30sccm, the pressure of the chamber is 0.3-1.0Pa, the applied current is 2-10A, and the deposition time is 20-80 min.
THE ADVANTAGES OF THE PRESENT INVENTION
The composite coating has strong binding force with the base material, can automatically block coating pinholes through metal oxidation in the corrosion process, effectively prevents corrosive media from permeating into a substrate, integrates the advantages of nitride conductivity and oxide passivation, and has better passivation effect on the premise of keeping certain conductivity. The composite coating can integrate the characteristic advantages of each layer, reduce the contact resistance and corrosion current of the metal plate base material and improve the durability of the metal plate.
Drawings
FIG. 1 is a schematic view of a bipolar plate according to the present invention;
in the figure, 1, a metal plate substrate, 2, a self-healing layer, 3, a compact corrosion-resistant layer, 4 and a conducting layer.
Detailed Description
Comparative example 1
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon to keep the pressure at 0.5Pa, applying a bias voltage of-600V on the sample to perform sputtering cleaning for 10min, and removing the surface oxide film.
The pressure of the chamber is kept unchanged, 30nm of titanium is deposited on the surface of the base material through the magnetron sputtering titanium target to serve as a self-healing layer, the current of the titanium target is 5A, and the deposition time is 5 min.
Introducing 18sccm nitrogen as reaction gas, adjusting the pressure of the chamber to 0.7Pa, and depositing 300nm titanium nitride as a conductive layer on the self-healing layer for 40 min.
The contact resistance between the bipolar plate and the carbon paper is 3.5m omega cm under 1.5MPa2At 0.5M H2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 8.6 muA/cm2。
Example 1
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon to keep the pressure at 0.5Pa, applying a bias voltage of-600V on the sample to perform sputtering cleaning for 10min, and removing the surface oxide film.
The pressure of the chamber is kept unchanged, 30nm of titanium is deposited on the surface of the base material through the magnetron sputtering titanium target to serve as a self-healing layer, the current of the titanium target is 5A, and the deposition time is 5 min.
Introducing 18sccm nitrogen and 3sccm oxygen as reaction gases, adjusting the pressure of the chamber to 0.7Pa, and depositing 100nm titanium oxynitride as a compact corrosion-resistant layer, wherein the oxygen atom number accounts for 9%, and the deposition time is 15 min.
Adjusting the oxygen flow to zero, and depositing 300nm titanium nitride on the compact corrosion-resistant layer as a conductive layer for 40 min.
The contact resistance between the bipolar plate and the carbon paper is 5.7m omega cm under 1.5MPa2At 0.5M H2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 2.5 muA/cm2Compared with the comparative example, the corrosion resistance is obviously improved. In addition, although the introduction of the oxynitride layer slightly increases the contact resistance, the resistance increase to such a degree does not substantially affect the water electrolysis system, and the improvement of the corrosion resistance is more critical.
Example 2
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon to keep the pressure at 0.5Pa, applying a bias voltage of-600V on the sample to perform sputtering cleaning for 10min, and removing the surface oxide film.
The pressure of the chamber is kept unchanged, 30nm of titanium is deposited on the surface of the base material through the magnetron sputtering titanium target to serve as a self-healing layer, the current of the titanium target is 5A, and the deposition time is 5 min.
Introducing 18sccm nitrogen and 4sccm oxygen as reaction gases, adjusting the pressure of the chamber to 0.7Pa, depositing 100nm titanium oxynitride as a dense corrosion-resistant layer, wherein the oxygen atom number accounts for 11%, and the deposition time is 15 min.
Adjusting the oxygen flow to zero, and depositing 300nm titanium nitride on the compact corrosion-resistant layer as a conductive layer for 40 min.
The contact resistance between the bipolar plate and the carbon paper is 8.9m omega cm under 1.5MPa2At 0.5MH2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 2.2 muA/cm2。
Example 3
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon gas to maintain pressureA bias voltage of-600V was applied to the sample at 0.5Pa for 10min to remove the surface oxide film.
The pressure of the chamber is kept unchanged, 30nm of titanium is deposited on the surface of the base material through the magnetron sputtering titanium target to serve as a self-healing layer, the current of the titanium target is 5A, and the deposition time is 5 min.
Introducing 18sccm nitrogen and 3sccm oxygen as reaction gases, adjusting the pressure of the chamber to 0.7Pa, depositing 100am titanium oxynitride as a compact corrosion-resistant layer, wherein the oxygen atom number accounts for 9%, and the deposition time is 15 min.
And stopping titanium target sputtering, adjusting the oxygen flow to zero, depositing 300nm niobium nitride on the compact corrosion-resistant layer as a conductive layer by magnetron sputtering niobium target, wherein the niobium target current is 5A, and the deposition time is 40 min.
The contact resistance between the bipolar plate and the carbon paper is 7.3m omega cm under 1.5MPa2At 0.5M H2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 4.4 muA/cm2。
Example 4
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon to keep the pressure at 0.5Pa, applying a bias voltage of-600V on the sample to perform sputtering cleaning for 10min, and removing the surface oxide film.
The pressure of the cavity is kept unchanged, 50nm titanium-niobium alloy is deposited on the surface of the base material to serve as a self-healing layer through magnetron sputtering of a titanium target and a niobium target, the current of the titanium target and the current of the niobium target are both 5A, and the deposition time is 6 min.
Stopping sputtering the niobium target, introducing 18sccm nitrogen and 3sccm oxygen as reaction gases, adjusting the pressure of the chamber to 0.7Pa, depositing 100nm titanium oxynitride as a compact corrosion-resistant layer, wherein the oxygen atom number accounts for 9%, and the deposition time is 15 min.
Adjusting the oxygen flow to zero, and depositing 300nm titanium nitride on the compact corrosion-resistant layer as a conductive layer for 40 min.
At 1.5MPa, in a reactorThe contact resistance between the bipolar plate and the carbon paper is 6.1m omega cm2At 0.5M H2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 2.5 muA/cm2。
Example 5
The method comprises the steps of selecting TA1 type pure titanium as a metal bipolar plate substrate, sequentially carrying out ultrasonic cleaning in deionized water and ethanol to remove surface dust and oil stains, naturally airing, and suspending in a vacuum chamber of a magnetron sputtering coating machine.
The chamber is evacuated to less than 3X 10-3Pa, introducing argon to keep the pressure at 0.5Pa, applying a bias voltage of-600V on the sample to perform sputtering cleaning for 10min, and removing the surface oxide film.
The pressure of the cavity is kept unchanged, 50nm titanium-niobium alloy is deposited on the surface of the base material to serve as a self-healing layer through magnetron sputtering of a titanium target and a niobium target, the current of the titanium target and the current of the niobium target are both 5A, and the deposition time is 6 min.
Stopping sputtering the titanium target, introducing 18sccm nitrogen and 3sccm oxygen as reaction gases, adjusting the pressure of the chamber to 0.7Pa, and depositing 100nm niobium oxynitride as a compact corrosion-resistant layer, wherein the oxygen atom number accounts for 7%, and the deposition time is 15 min.
And adjusting the oxygen flow to zero, and depositing 300am of niobium nitride as a conductive layer on the compact corrosion-resistant layer for 40 min.
The contact resistance between the bipolar plate and the carbon paper is 7.7m omega cm under 1.5MPa2At 0.5M H2SO4+5ppm F-The polarization current at the lower constant potential of 1.8V (vs. SCE) is 3.9 muA/cm2。
In the embodiment, the contact resistance and the corrosion current of the TA1 type pure titanium modified by the composite coating prepared by the scheme are smaller than the numerical values before modification (10.6m omega cm)2，9.5μA/cm2) The composite coating can obviously improve the conductivity and corrosion resistance of the metal plate.
Claims (10)
1. The composite coating for the water electrolysis metal bipolar plate is characterized by comprising a self-healing layer and an anti-corrosion layer which are alternately arranged along the surface of the metal bipolar plate to the outside in sequence, wherein the self-healing layer and the anti-corrosion layer are alternated at least once, and the outermost layer is a conducting layer;
the self-healing layer is one or more than two alloys of titanium, zirconium, niobium, chromium and tantalum;
the corrosion-resistant layer is a transition metal oxynitride layer, wherein the transition metal oxynitride comprises at least one of titanium oxynitride, zirconium oxynitride and niobium oxynitride, and the atomic ratio of oxygen atoms is 1-20%;
the conducting layer is a transition metal nitride layer, wherein the transition metal nitride comprises at least one of titanium nitride, zirconium nitride, niobium nitride, chromium nitride and niobium nitride.
2. The composite coating according to claim 1, wherein the transition metal oxynitride has an atomic ratio of oxygen atoms of 5% to 15%.
3. The composite coating according to claim 1, wherein the self-healing layer has a thickness of 20 to 200nm, the dense corrosion resistant layer has a thickness of 20 to 300nm, and the conductive layer has a thickness of 50 to 800 nm.
4. The composite coating according to claim 3, wherein the self-healing layer has a thickness of 30-100nm, the corrosion-resistant layer has a thickness of 50-200nm, and the conductive layer has a thickness of 100-500 nm.
5. A method for preparing a composite coating according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) pretreating the metal bipolar plate base material to remove surface stains and an oxide film;
(2) sequentially and alternately depositing a self-healing layer and an anti-corrosion layer on the surface of the pretreated metal bipolar plate base material; the preparation method of the self-healing layer comprises at least one of ion implantation, magnetron sputtering, multi-arc ion plating and plasma spraying; the method for manufacturing the corrosion-resistant layer comprises at least one of magnetron sputtering, multi-arc ion plating and atomic layer deposition;
(3) depositing a conductive layer on the surface of the outermost corrosion-resistant layer deposited in the step (2); the preparation method of the conducting layer comprises at least one of magnetron sputtering, multi-arc ion plating and plasma spraying.
6. The method for preparing the composite coating according to claim 5, wherein the step (1) comprises the steps of: sequentially carrying out water washing and alcohol washing on the metal bipolar plate substrate to remove surface stains, and then cleaning and removing a surface oxidation film through magnetron sputtering; in the sputtering cleaning process, the pressure of the chamber is 0.3-1.0Pa, the applied voltage is-500V to-800V, and the cleaning time is 5-30 min.
7. The method for preparing a composite coating according to claim 5, wherein the one-time alternation of the self-healing layer and the corrosion resistant layer in the step (2) comprises the steps of: depositing a self-healing layer by a magnetron sputtering method, introducing nitrogen and oxygen as reaction gases after the deposition of the self-healing layer is finished, and depositing an anti-corrosion layer on the surface of the self-healing layer by magnetron sputtering;
wherein, in the deposition process of the self-healing layer, the pressure of the cavity is 0.3-1.0Pa, the applied current is 2-8A, and the deposition time is 3-30 min; n; in the process of depositing the corrosion-resistant layer, the flow rates of nitrogen and oxygen are respectively 10-30sccm and 2-10sccm, the pressure of the chamber is 0.3-1.0Pa, the applied current is 2-10A, and the deposition time is 10-40 min.
8. The method for preparing the composite coating according to claim 5, wherein the step (3) comprises the steps of: taking nitrogen as reaction gas, and depositing a conductive layer by magnetron sputtering; the nitrogen flow is 10-30seem, the chamber pressure is 0.3-1.0Pa, the applied current is 2-10A, and the deposition time is 20-80 min.
9. A water electrolysed metallic bipolar plate, characterized in that it comprises a composite coating according to any one of claims 1 to 4.
10. Use of a metallic bipolar plate according to claim 9 in a water electrolysis device.
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