CN115011987A - Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof - Google Patents

Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof Download PDF

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CN115011987A
CN115011987A CN202210923698.9A CN202210923698A CN115011987A CN 115011987 A CN115011987 A CN 115011987A CN 202210923698 A CN202210923698 A CN 202210923698A CN 115011987 A CN115011987 A CN 115011987A
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protective layer
base material
bipolar plate
hydrogen production
corrosion
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CN115011987B (en
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王鹏杰
王金意
任志博
王韬
巩玉栋
张畅
余智勇
徐显明
张欢
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Huaneng Clean Energy Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/036—Bipolar electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention discloses an anticorrosive bipolar plate for hydrogen production by water electrolysis, and a preparation method and equipment thereof, wherein the preparation method comprises the following steps: carrying out electrifying dipping treatment on the first base material to obtain a second base material; ultrasonically washing and drying the second base material, and treating by adopting high-energy airflow to obtain a third base material; at least two protective layers are formed on the surface of the third base material, the outermost protective layer is removed, after each protective layer is formed, the third base material containing the protective layer is processed by the second base material to obtain the third base material, and then the next protective layer is formed. The preparation method of the water electrolysis hydrogen production anti-corrosion bipolar plate can enhance the binding force between the base material and the protective layers and between the protective layers, so that the prepared bipolar plate can be widely applied to environments with high voltage, oxygen, high humidity and acidic conditions.

Description

Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof
Technical Field
The invention relates to the technical field of hydrogen production, in particular to an anticorrosive bipolar plate for hydrogen production by water electrolysis and a preparation method and equipment thereof.
Background
Currently, a new round of energy technology revolution is being started worldwide, and the international energy pattern is also changing profoundly. In view of the strategic role of hydrogen energy in the future energy and environment fields, in recent years, the government of China has emphasized the strategic position of hydrogen energy many times, in the year 2020 and 04, the national energy agency has issued "energy law of the people's republic of China (draft for comments), and hydrogen energy is formally incorporated into the definition of energy. In the technical route of hydrogen preparation, the technology of hydrogen production by water electrolysis with high efficiency, no pollution and sustainable renewable energy is the most environment-friendly, and the prepared hydrogen becomes green hydrogen.
The water electrolysis hydrogen production technology can be roughly divided into three categories: firstly, an alkaline water electrolysis hydrogen production technology; the second is a Proton Exchange Membrane (PEM) hydrogen production technology by water electrolysis; thirdly, a Solid Oxide Electrolytic Cell (SOEC) electrolyzes water to produce hydrogen. The PEM hydrogen production technology uses pure water as a raw material, has high response speed and high hydrogen production efficiency, is particularly suitable for matching the characteristics of volatility and intermittency of renewable energy sources, and is a main hydrogen production technology developed in the future.
The equipment for producing hydrogen by water electrolysis is an electrolytic cell, and water can be electrolyzed into hydrogen and oxygen by electric energy. Hydrogen and oxygen are located on either side of the bipolar plate. The bipolar plate is one of the core components of the electrolytic cell and directly influences the performance of the whole electrolytic cell. Because the inside of the electrolytic cell is high voltage, oxygen environment, high humidity and acidic condition, common metal is easy to corrode under the condition, and the electrolytic cell fails. At present, some bipolar plates are formed by injection molding of a non-metal frame bipolar plate to replace a metal plate frame, so that corrosion is avoided to a certain extent, and cost is reduced, but a part of metal is still required to be used as a metal separator, and the problem of metal corrosion is not solved; other bipolar plates are formed by adhering a flexible graphite thin layer or a graphene thin layer to the surface of a metal thin plate, the contact resistance can be effectively reduced by the method, but the graphite can generate oxidation reaction in a high-potential oxygen environment, so that the problem of corrosion of a metal polar plate cannot be solved; in still other bipolar plates, a passivation layer (one or two alloys of titanium, tungsten, zirconium, vanadium, niobium, tantalum, and molybdenum), a support layer (nitrogen-doped transition metal carbide layer), and a corrosion-resistant conductive layer (nitrogen-doped carbon layer) are sequentially disposed on the metal surface, which can effectively prevent corrosion under low-voltage (less than 1V) aerobic environment, but can still generate oxidation reaction of the carbon layer under high-voltage (more than 1.5V) aerobic environment, and can not effectively prevent metal corrosion.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing an anticorrosive bipolar plate by electrolyzing water to produce hydrogen, which comprises performing an electrical immersion treatment and an ultrasonic washing treatment on a substrate, performing an ultrasonic washing treatment on the surface of each protective layer except the outermost protective layer, and performing an ultrasonic washing treatment and a high-energy gas treatment on the surface of each protective layer, so as to enhance the bonding force between the substrate and each protective layer and between the protective layers, and thus the prepared bipolar plate can be widely applied to environments under high-voltage, aerobic, high-humidity and acidic conditions.
The invention also aims to provide the anti-corrosion bipolar plate for hydrogen production by water electrolysis.
Still another object of the present invention is to provide an apparatus for producing hydrogen by electrolyzing water.
In order to achieve the above object, a first embodiment of the present invention provides a method for preparing an anti-corrosion bipolar plate for hydrogen production by water electrolysis, which comprises:
carrying out electrifying dipping treatment on the first base material to obtain a second base material;
ultrasonically washing and drying the second base material, and treating by adopting high-energy airflow to obtain a third base material;
at least two protective layers are formed on the surface of the third base material, and except the outermost protective layer, after each protective layer is formed, the third base material containing the protective layer is processed by the second base material to obtain the third base material, and then the next protective layer is formed.
In some embodiments of the present invention, the first substrate is one or an alloy of two or more of stainless steel, iron, aluminum, copper, and nickel.
In some embodiments of the present invention, the impregnation solution used in the electrified impregnation treatment is a mixed solution of acetone and sulfuric acid. Preferably, the mixing mass ratio of the acetone to the sulfuric acid is 1:1-19: 1.
In some embodiments of the invention, the voltage of the electrification and immersion treatment is between 0.8 and 1.2V, the time of the electrification and immersion treatment is 10 to 60min, and the counter electrode of the electrification and immersion treatment is one of a graphite electrode and a platinum electrode.
In some embodiments of the invention, the high energy gas stream is one of high energy carbon dioxide, nitrogen, argon, air.
In some embodiments of the invention, the high energy gas stream is treated for 10-30min at a pressure of 5-200 MPa.
In some embodiments of the present invention, the material of the protective layer is one or more of non-metal or metal.
In some embodiments of the present invention, the materials used for the protective layers are different, and the thickness of each protective layer increases sequentially from the side close to the third substrate surface to the side far from the third substrate surface.
In some embodiments of the present invention, the number of the protective layers is three, and a first protective layer, a second protective layer and a third protective layer are sequentially disposed from a side close to the third substrate surface to a side far away from the third substrate surface;
the first protective layer is made of nonmetal or metal, the second protective layer is made of one or more of carbon, nitrogen, titanium and silver, and the third protective layer is made of noble metal.
In some embodiments of the present invention, the material of the first protective layer is one of carbon, nitrogen, titanium, tungsten, zirconium, vanadium, niobium, tantalum, and molybdenum.
In some embodiments of the present invention, the first protective layer is a titanium metal layer with a thickness of less than 10 nm; the second protective layer is an Ag/Ti alloy layer, and the thickness of the second protective layer is less than 20 nm; the third protection layer is a noble metal layer, and the thickness of the third protection layer is less than 50 nm.
In some embodiments of the present invention, the method for forming the protective layer on the surface of the third substrate is vapor deposition or electrodeposition. Preferably, the method for forming the protective layer on the surface of the third substrate is vacuum plating, and the process condition of the vacuum degree is as follows: ambient temperature: 10-30 ℃, relative humidity: not more than 70%, cooling water inlet temperature: not higher than 25 ℃; degree of vacuum (10X 10) -1 ）-（8×10 -4 ）Pa。
In order to achieve the above purpose, a second aspect of the present invention provides an electrolytic water hydrogen production anticorrosive bipolar plate, which is prepared by the preparation method of the electrolytic water hydrogen production anticorrosive bipolar plate according to the embodiment of the present invention.
In order to achieve the purpose, the embodiment of the third aspect of the invention provides a water electrolysis hydrogen production device, which comprises the water electrolysis hydrogen production anti-corrosion bipolar plate.
The preparation method of the water electrolysis hydrogen production anticorrosion bipolar plate provided by the embodiment of the invention has the following beneficial effects:
the base material is subjected to electrifying dipping treatment and ultrasonic washing and then high-energy airflow treatment, and the surfaces of all the protective layers except the outermost protective layer are subjected to ultrasonic washing and high-energy airflow treatment, so that the binding force between the base material and the protective layers and between the protective layers can be enhanced, and the prepared bipolar plate can be widely applied to environments with high voltage, oxygen, high humidity and acidic conditions.
The beneficial effects of the water electrolysis hydrogen production corrosion-resistant bipolar plate and the water electrolysis hydrogen production equipment in the embodiment of the invention are basically the same as the beneficial effects of the preparation method of the water electrolysis hydrogen production corrosion-resistant bipolar plate in the embodiment of the invention, and are not repeated herein.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic diagram of a simple structure of a bipolar plate for hydrogen production by electrolysis of water according to an embodiment of the present invention.
FIG. 2 is a surface topography map (SEM image) of a first substrate in example 1 of the present invention.
FIG. 3 is a surface topography map (SEM image) of a second substrate in example 1 of the present invention.
FIG. 4 is a surface topography map (SEM image) of a third substrate in example 1 of the present invention.
FIG. 5 is a graph comparing the corrosion resistance of the water electrolysis hydrogen production corrosion-resistant bipolar plate prepared by the preparation method of example 1 of the present invention and a comparative sample.
Fig. 6 is a schematic diagram of a simple structure of an apparatus for producing hydrogen by electrolyzing water according to an embodiment of the present invention.
Fig. 7 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis and corrosion protection by water prepared by the preparation method of the embodiment 1 after 1000 hours of use.
FIG. 8 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis of water and corrosion protection prepared by the preparation method of comparative example 1 after 1000 hours of use.
FIG. 9 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis of water and corrosion protection prepared by the preparation method of comparative example 2 after 1000 h.
FIG. 10 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis of water and corrosion protection prepared by the preparation method of comparative example 3 after 1000 h.
Reference numerals:
1-a substrate layer; 2-a first protective layer; 3-a second protective layer; 4-third protective layer; 6-a first bipolar plate; 7-a first diffusion layer; 8-a membrane electrode; 9-a second diffusion layer; 10-a second bipolar plate; 11-sealing ring.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The raw materials and equipment related to the examples and comparative examples of the present invention are commercially available raw materials and equipment unless otherwise specified; the methods according to the examples of the present invention and comparative examples are conventional experimental methods unless otherwise specified.
The preparation method of the corrosion-resistant bipolar plate for hydrogen production by water electrolysis comprises the following steps
Carrying out electrifying dipping treatment on the first base material to obtain a second base material;
ultrasonically washing and drying the second base material, and treating by adopting high-energy airflow to obtain a third base material;
at least two protective layers are formed on the surface of a third base material, except the outermost protective layer, after each protective layer is formed, the third base material containing the protective layer is processed by obtaining the third base material from the second base material, and then the next protective layer is formed.
According to the preparation method of the water electrolysis hydrogen production anti-corrosion bipolar plate, the base material is subjected to high-energy airflow treatment after electrification impregnation treatment and ultrasonic washing, and the surfaces of all the protective layers except the outermost protective layer are subjected to ultrasonic washing and high-energy airflow treatment, so that the binding force between the base material and the protective layers and between the protective layers can be enhanced, and the prepared bipolar plate can be widely applied to environments with high voltage, oxygen, high humidity and acidic conditions.
In some embodiments of the invention, the ultrasonic washing may be washed with distilled water.
In some embodiments, the first substrate is one of stainless steel, iron, aluminum, copper, and nickel; in other embodiments, the first substrate may be an alloy of two or more of stainless steel, iron, aluminum, copper, and nickel.
In some embodiments, the impregnation liquid used in the electrification impregnation treatment can be a mixed solution of acetone and sulfuric acid, for example, a mixed solution of acetone and sulfuric acid in a mass ratio of 1:1-19: 1. In other embodiments, the impregnation liquid used in the electrified impregnation treatment can also be an aqueous oxalic acid solution. In general, the electrical immersion may be performed at normal temperature.
In some embodiments, the voltage of the electrifying and dipping treatment is between 0.8 and 1.2V, the time of the electrifying and dipping treatment is 10 to 60min, and the counter electrode of the electrifying and dipping treatment is one of a graphite electrode and a platinum electrode.
The principle of the electrification impregnation treatment is as follows: the selected metal substrate lattice is a tetragonal structure, a hexagonal structure or an octahedral structure, when electrochemical treatment is carried out, reaction point positions of the base material can be carried out by taking the lattice as a unit, two choices are generally provided, one choice is carried out at a crystal boundary between the lattices, the other choice is carried out at a lattice center, and two different types of reactions at the interface between the lattices and the lattice center of the lattice can be realized by controlling voltage and the type of electrolyte.
In some embodiments, the high energy gas stream is one of high energy carbon dioxide, nitrogen, argon, air. And treating the ultrasonically-washed and dried second base material by adopting high-energy airflow for 10-30min, wherein the pressure is 5-200 MPa.
In some embodiments, the material of the protective layer may be one or more of a nonmetal, a metal, a noble metal, or a metal, for example, the nonmetal may be carbon, nitrogen, or the like, and the metal may be titanium, tungsten, zirconium, vanadium, niobium, tantalum, molybdenum, or the like. As a possible example, the materials used for the protective layers are different, and taking the number of the protective layers as three layers as an example, the first protective layer, the second protective layer and the third protective layer are defined in sequence from the side close to the surface of the third substrate to the side far from the surface of the third substrate, the first protective layer may be made of non-metal or metal, such as one or more of carbon, nitrogen, titanium, tungsten, zirconium, vanadium, niobium, tantalum, molybdenum, etc., the second protective layer may be made of one or more of carbon, nitrogen, titanium, silver, such as an Ag/Ti alloy layer, etc., and the third protective layer may be made of noble metal, such as one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.
In some embodiments, the thickness of each overcoat layer may be equal; in other embodiments, the thickness of each protective layer increases from the side near the third substrate surface to the side far from the third substrate surface. Still taking the case of three layers as an example of the number of protective layers described above, as a possible example, the first protective layer is a titanium metal layer, with a thickness of less than 10 nm; the second protective layer is an Ag/Ti alloy layer, and the thickness of the second protective layer is less than 20 nm; the third protection layer is a noble metal layer, and the thickness of the third protection layer is less than 50 nm.
In some embodiments, the method for forming the protective layer on the surface of the third substrate is vapor deposition or electrodeposition, and as a possible example, the method for forming the protective layer on the surface of the third substrate is vacuum plating in vapor deposition, and the process parameters can be selected as follows: ambient temperature: 10-30 ℃, relative humidity: not more than 70%, cooling water inlet temperature: vacuum degree (10X 10) of not higher than 25 deg.C -1 ）-（8×10 -4 ）Pa。
In the invention, after each protective layer is formed, ultrasonic washing and high-energy airflow treatment are adopted, and a sub-nanometer rough surface is formed on the surface of the corresponding protective layer after treatment, so that the interface bonding force is increased, and the bonding between two adjacent protective layers is firmer.
The water electrolysis hydrogen production anticorrosion bipolar plate provided by the embodiment of the invention is prepared by adopting the preparation method of the water electrolysis hydrogen production anticorrosion bipolar plate provided by the embodiment of the invention.
As a possible example, the corrosion-resistant bipolar plate for hydrogen production by electrolysis of water according to the embodiment of the present invention includes a base layer (here, the base layer may be understood as a third base material obtained by treating the first base material in the above-mentioned preparation method), and the surface of the base layer is sequentially provided with at least 2 protective layers from a side close to the base layer to a side away from the base layer. In some embodiments, the material of the protective layer is selected according to three principles: (1) has the corrosion resistance; (2) the number of layers of the protective layer is as small as possible, and the thickness of the protective layer is as thin as possible, so that the surface resistance is reduced; (3) has conductive performance. The protective layer may be made of one or more of non-metal and metal, for example, carbon and nitrogen may be used as the non-metal, and titanium, tungsten, zirconium, vanadium, niobium, tantalum, molybdenum, noble metal, etc. may be used as the metal. As a possible example, the materials used for the protective layers are different, and taking the number of the protective layers as three layers (as shown in fig. 1), the first protective layer 2, the second protective layer 3 and the third protective layer 4 are defined in sequence from the side close to the surface of the base layer 1 to the side far from the surface of the base layer, the material of the first protective layer 2 may be a non-metal or a metal, such as one or more of carbon, nitrogen, titanium, tungsten, zirconium, vanadium, niobium, tantalum, molybdenum, etc., the material of the second protective layer 3 may be one or more of carbon, nitrogen, titanium, silver, such as an Ag/Ti alloy layer, etc., the material of the third protective layer 4 may be a noble metal, such as one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc. In some embodiments, the thickness of each overcoat layer may be equal; in other embodiments, the thickness of each protective layer increases from the side near the surface of the substrate layer 1 to the side far from the surface of the substrate layer. Still taking the case of three layers as an example of the number of protective layers described above, as a possible example, the first protective layer 2 is a titanium metal layer, with a thickness of less than 10 nm; the second protective layer 3 is an Ag/Ti alloy layer, and the thickness is less than 20 nm; the third protective layer 4 is a noble metal layer, and the thickness is less than 50 nm.
It should be noted that, in the bipolar plate for hydrogen production by electrolysis of water and corrosion prevention of the embodiment of the present invention, the number of the protective layers and the material of each protective layer may be set and selected according to actual needs, for example, the requirement for corrosion prevention is high, the number of the protective layers may be correspondingly large, and the material of each protective layer should be selected according to the premise that the material of each protective layer has conductive corrosion prevention performance, the closer to the base layer, the better the conductive performance is, and the farther away from the base layer, the better the corrosion prevention performance is. Finally, requirements and cost such as actual corrosion prevention are combined, the number of the protective layers is set, and corresponding protective layer materials are selected.
The water electrolysis hydrogen production anti-corrosion bipolar plate provided by the embodiment of the invention can be widely applied to water electrolysis hydrogen production, in particular to water electrolysis hydrogen production equipment.
The water electrolysis hydrogen production equipment comprises the water electrolysis hydrogen production anti-corrosion bipolar plate according to the embodiment of the invention. As a possible example, as shown in fig. 6, the water electrolysis hydrogen production apparatus according to the embodiment of the present invention includes a first bipolar plate 6, a first diffusion layer 7, a membrane electrode 8, a second diffusion layer 9, and a second bipolar plate 10, which are sequentially arranged from top to bottom and are mounted together through a sealing ring 11; wherein: the first bipolar plate 6 and the second bipolar plate 10 are both the water electrolysis hydrogen production anti-corrosion bipolar plates of the embodiment of the invention, and the base layer of the first bipolar plate 6 is tightly attached to the first diffusion layer 7, and the base layer of the second bipolar plate 10 is tightly attached to the second diffusion layer 9; the first diffusion layer 7 and the second diffusion layer 9 can both adopt the diffusion layer structure and material of the existing conventional water electrolysis hydrogen production equipment, for example, the first diffusion layer can adopt porous titanium, and the second diffusion layer can adopt carbon paper; the membrane electrode 8 can also adopt the membrane electrode structure and material of the existing conventional water electrolysis hydrogen production equipment; the sealing ring can be a conventional fluorine rubber sealing ring and the like. The implementation manner of mounting the first bipolar plate, the first diffusion layer, the membrane electrode, the second diffusion layer and the second bipolar plate together through the seal ring is the prior art, and is not described herein again.
The invention relates to a water electrolysis hydrogen production anti-corrosion bipolar plate, a preparation method and application thereof, which are described in the following by combining specific examples.
Example 1
As shown in fig. 1, the water electrolysis hydrogen production anticorrosion bipolar plate of the embodiment includes a substrate layer 1, a first protection layer 2, a second protection layer 3 and a third protection layer 4, which are sequentially arranged from bottom to top, wherein: the substrate layer 1 is made of a stainless steel plate; the first protective layer 2 is a titanium metal layer and has the thickness of 5 nm; the second protective layer 3 is an Ag/Ti alloy layer, wherein the mass ratio of Ag to Ti is 1:1, the thickness of the second protective layer 3 is 10 nm; the third protection layer 4 is a platinum metal layer with a thickness of 25 nm.
The preparation method of the corrosion-resistant bipolar plate for hydrogen production by water electrolysis comprises the following steps:
(1) and (3) immersing the first base material of the stainless steel plate into a mixed solution of acetone and sulfuric acid in a mass ratio of 9.5:1, applying a voltage of 1.0V between the stainless steel base layer and the counter electrode graphite, and treating for 35min to obtain a second base material. Compared with the first substrate (shown in FIG. 2), the second substrate (shown in FIG. 3) has many more protrusions, and the protrusions form multiple channels of 1-50 nm.
(2) And ultrasonically washing the second base material in distilled water for 10min, drying in a drying box, and then treating the second base material for 20min at 100MPa by adopting high-energy carbon dioxide gas to obtain a third base material. Compared with the second substrate (shown in fig. 3), the third substrate (shown in fig. 4) has nanometer-scale channels at the bottom of the surface protrusions, so that the bonding force is stronger.
(3) Forming a first protective layer on the surface of the third base material by adopting a vacuum plating method to obtain a first plating plate, wherein the process conditions of the vacuum plating are as follows: ambient temperature: 20 ℃, relative humidity: 60%, cooling water inlet temperature: vacuum degree of 8X 10 at 20 DEG C -3 Pa。
(4) And ultrasonically washing the first plating plate in distilled water for 10min, blowing and drying, and then treating the first plating plate at 100MPa for 20min by adopting high-energy carbon dioxide gas.
(5) Forming a second protective layer on the surface of the first protective layer of the first plating plate treated in the step (4) by adopting a vacuum plating method to obtain a second plating plate, wherein the process conditions of vacuum plating are as follows: ambient temperature: 20 ℃, relative humidity: 60%, cooling water inlet temperature: vacuum degree of 2X 10 at 20 DEG C -3 Pa。
(6) And ultrasonically washing the second plating plate in distilled water for 10min, blowing and drying, and then treating the second plating plate at 100MPa for 20min by adopting high-energy carbon dioxide gas.
(7) And (3) forming a third protection layer on the surface of the second protection layer of the second plating plate treated in the step (6) by adopting a vacuum plating method to obtain the water electrolysis hydrogen production corrosion-resistant bipolar plate of the embodiment of the invention, wherein the process conditions of vacuum plating are as follows: ambient temperature: 20 ℃, relative humidity: 60%, cooling water inlet temperature: vacuum degree of 1X 10 at 20 DEG C -3 Pa。
The water electrolysis hydrogen production anti-corrosion bipolar plate of the embodiment and a comparative sample (one bipolar plate product sold in the market at present) are tested in a 0.5mol sulfuric acid solution +10ppm F-solution,the voltage was swept from-0.2V to 1.0V at a sweep rate of 2mV/s, and the results are shown in FIG. 5. As can be seen from FIG. 5, the corrosion current of the bipolar plate for hydrogen production by electrolysis of water and corrosion prevention prepared by the preparation method of the embodiment of the invention is 10 -6 A/cm 2 Comparison sample 10 -4 A/cm 2 Two orders of magnitude reduction.
Fig. 7 is a surface topography (scanning electron microscope image) of the bipolar plate for hydrogen production by electrolysis and corrosion prevention by water prepared by the preparation method of example 1 after 1000 hours of use. As can be seen from fig. 7, the surface of the third protection layer of the bipolar plate for hydrogen production by electrolysis of water has no bubbling or peeling after 1000h of use.
Example 2
This embodiment is substantially the same as embodiment 1 except that:
in the preparation method of the water electrolysis hydrogen production anticorrosion bipolar plate, the voltage in the step (1) is 0.9V, and the treatment time is 15 min.
Example 3
This embodiment is substantially the same as embodiment 1 except that:
in the method for preparing the corrosion-resistant bipolar plate by electrolyzing water to prepare hydrogen, the voltage in the step (1) is 1.1V, and the treatment time is 55 min.
Example 4
This embodiment is substantially the same as embodiment 1 except that:
in the method for preparing the corrosion-resistant bipolar plate by electrolyzing water to prepare hydrogen, the ultrasonic washing conditions in the steps (2), (4) and (6) are as follows: the washing time was 15 min.
Example 5
This embodiment is substantially the same as embodiment 1 except that:
in the method for preparing the corrosion-resistant bipolar plate by electrolyzing water to prepare hydrogen, the ultrasonic washing conditions in the steps (2), (4) and (6) are as follows: the washing time was 20 min.
Example 6
This embodiment is substantially the same as embodiment 1 except that:
in the preparation method of the corrosion-resistant bipolar plate for hydrogen production by electrolyzing water, the pressure for the treatment with the high-energy carbon dioxide gas in the steps (2), (4) and (6) is 10MPa, and the treatment time is 10 min.
Example 7
This embodiment is substantially the same as embodiment 1 except that:
in the preparation method of the corrosion-resistant bipolar plate for hydrogen production by electrolyzing water, the pressure for the treatment with the high-energy carbon dioxide gas in the steps (2), (4) and (6) is 180MPa, and the treatment time is 28 min.
Example 8
This embodiment is substantially the same as embodiment 1 except that:
in the water electrolysis hydrogen production anticorrosion bipolar plate of the embodiment, the base layer is aluminum, the thickness of the first protective layer is 9nm, the thickness of the second protective layer is 18nm, and the thickness of the third protective layer is 40 nm.
In the preparation method of the water electrolysis hydrogen production anticorrosion bipolar plate, in the step (1), the impregnation solution is a mixed solution of acetone and sulfuric acid in a mass ratio of 1: 1; the process conditions of vacuum plating in the step (3) are as follows: ambient temperature: 10 ℃, relative humidity: 50%, cooling water inlet temperature: vacuum degree of 4X 10 at 10 DEG C -3 Pa; the process conditions of vacuum plating in the step (5) are the following ambient temperature: 10 ℃, relative humidity: 50%, cooling water inlet temperature: vacuum degree of 1.5X 10 at 10 DEG C -3 Pa; the process conditions of vacuum plating in the step (7) are the following ambient temperature: 10 ℃, relative humidity: 50%, cooling water inlet temperature: vacuum degree of 9X 10 at 10 DEG C -4 Pa。
Example 9
The water electrolysis hydrogen production anticorrosion bipolar plate of this embodiment includes stratum basale, first inoxidizing coating and the second inoxidizing coating that top-down set gradually, wherein: the base layer adopts a copper plate; the first protective layer is a titanium metal layer and has the thickness of 2 nm; the second protective layer is an Ag/Ti alloy layer, wherein the mass ratio of Ag to Ti is 1:1, the thickness of the second protective layer is 5 nm.
The preparation method of the corrosion-resistant bipolar plate for hydrogen production by water electrolysis comprises the following steps:
(1) and (3) immersing the first base material of the copper plate into a mixed solution of acetone and sulfuric acid in a mass ratio of 18:1, and applying a voltage of 0.9V between the stainless steel base layer and the counter electrode platinum for treatment for 35min to obtain a second base material.
(2) And ultrasonically washing the second base material in distilled water for 20min, drying the second base material in a drying box, and then treating the second base material at 100MPa for 20min by adopting high-energy nitrogen to obtain a third base material.
(3) Forming a first protective layer on the surface of the third base material by adopting a vacuum plating method to obtain a first plating plate, wherein the process conditions of the vacuum plating are as follows: ambient temperature: 15 ℃, relative humidity: 50%, cooling water inlet temperature: vacuum degree of 7X 10 at 10 DEG C -3 Pa。
(4) And ultrasonically washing the first plating plate in distilled water for 20min, blowing and drying, and then treating the first plating plate at 100MPa for 20min by adopting high-energy carbon dioxide gas.
(5) And (3) forming a second protective layer on the surface of the first protective layer of the first plating plate treated in the step (4) by adopting a vacuum plating method to obtain the water electrolysis hydrogen production anti-corrosion bipolar plate of the embodiment of the invention, wherein the process conditions of the vacuum plating are as follows: ambient temperature: 15 ℃, relative humidity: 50%, cooling water inlet temperature: vacuum degree of 3X 10 at 10 DEG C -3 Pa。
Comparative example 1
This comparative example is essentially the same as example 1, except that:
the method for preparing the corrosion-resistant bipolar plate by electrolyzing water to prepare hydrogen does not comprise the step (1), and the stainless steel plate is directly subjected to ultrasonic cleaning.
FIG. 8 is a surface topography (scanning electron microscope image) of the water electrolysis hydrogen production anti-corrosion bipolar plate prepared by the preparation method of comparative example 1 after 1000 hours of use. As can be seen from FIG. 8, the bipolar plate for hydrogen production by electrolysis of water and corrosion protection of the comparative example has a large amount of bubbles and shedding after 1000h of use.
Comparative example 2
This comparative example is essentially the same as example 1, except that:
the method for manufacturing the corrosion-resistant bipolar plate by electrolyzing water to produce hydrogen does not comprise the high-energy carbon dioxide gas treatment process in the step (2).
FIG. 9 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis of water and corrosion protection prepared by the preparation method of comparative example 2 after 1000 h. As can be seen from FIG. 9, the comparative example water electrolysis hydrogen production anti-corrosion bipolar plate has a small amount of bubbles and shedding after 1000h of use.
Comparative example 3
This comparative example is essentially the same as example 1, except that:
the preparation method of the water electrolysis hydrogen production anti-corrosion bipolar plate does not comprise the step (4) and the step (6), namely, the vacuum plating method is adopted to form the first protective layer on the surface of the third base material, then ultrasonic washing and high-energy carbon dioxide treatment are not carried out, the second protective layer is directly formed, and after the second protective layer is formed, ultrasonic washing and high-energy carbon dioxide treatment are not carried out, and the third protective layer is directly formed.
FIG. 10 is a surface topography (scanning electron microscope) of the bipolar plate for hydrogen production by electrolysis of water and corrosion protection prepared by the preparation method of comparative example 3 after 1000 h. As can be seen from FIG. 9, the comparative example water electrolysis hydrogen production anti-corrosion bipolar plate has a small amount of bubbles and shedding after 1000h of use.
In summary, according to the preparation method of the bipolar plate for hydrogen production by electrolysis, the prepared bipolar plate for hydrogen production by electrolysis has better binding force between the protective layers and the substrate layer and between the protective layers, and has excellent corrosion resistance.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (12)

1. The preparation method of the water electrolysis hydrogen production anti-corrosion bipolar plate is characterized by comprising the following steps
Carrying out electrifying dipping treatment on the first base material to obtain a second base material;
ultrasonically washing and drying the second base material, and treating by adopting high-energy airflow to obtain a third base material;
at least two protective layers are formed on the surface of the third base material, and except the outermost protective layer, after each protective layer is formed, the third base material containing the protective layer is processed by the second base material to obtain the third base material, and then the next protective layer is formed.
2. The production method according to claim 1, wherein the first base material is one or an alloy of two or more of stainless steel, iron, aluminum, copper, and nickel; the impregnation liquid used for the electrification impregnation treatment is a mixed solution of acetone and sulfuric acid.
3. The preparation method according to claim 1, wherein the voltage of the electrifying and dipping treatment is between 0.8 and 1.2V, the time of the electrifying and dipping treatment is between 10 and 60min, and the counter electrode of the electrifying and dipping treatment is one of a graphite electrode and a platinum electrode.
4. The method of claim 1, wherein the high energy gas stream is one of high energy carbon dioxide, nitrogen, argon, air.
5. The method according to claim 1, wherein the high-energy gas stream is treated for 10-30min at a pressure of 5-200 MPa.
6. The method according to claim 1, wherein the protective layer is made of one or more of a non-metal or a metal.
7. The method according to claim 1, wherein the protective layers are made of different materials, and the thickness of each protective layer increases from the side close to the surface of the third substrate to the side far from the surface of the third substrate.
8. The preparation method according to claim 1, wherein the number of the protective layers is three, and the first protective layer, the second protective layer and the third protective layer are arranged in sequence from the side close to the surface of the third substrate to the side far away from the surface of the third substrate;
the material of first inoxidizing coating is nonmetal or metal, the material of second inoxidizing coating is one or more than two in carbon, nitrogen, titanium, the silver, the material of third inoxidizing coating is noble metal.
9. The method according to claim 8, wherein the first protective layer is made of one of carbon, nitrogen, titanium, tungsten, zirconium, vanadium, niobium, tantalum, and molybdenum.
10. The method according to claim 1, wherein the protective layer is formed on the surface of the third substrate by vapor deposition or electrodeposition.
11. An anti-corrosion bipolar plate for hydrogen production by electrolysis of water, which is produced by the production method according to any one of claims 1 to 10.
12. An apparatus for producing hydrogen by electrolyzing water, comprising the bipolar plate for producing hydrogen by electrolyzing water as claimed in claim 11.
CN202210923698.9A 2022-08-02 2022-08-02 Water electrolysis hydrogen production anti-corrosion bipolar plate and preparation method and equipment thereof Active CN115011987B (en)

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