CN117051424A - Gas diffusion layer with pore structure, surface modification method and application - Google Patents
Gas diffusion layer with pore structure, surface modification method and application Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 50
- 239000011148 porous material Substances 0.000 title claims abstract description 36
- 238000002715 modification method Methods 0.000 title description 5
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- 238000000576 coating method Methods 0.000 claims abstract description 111
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 105
- 239000002184 metal Substances 0.000 claims abstract description 105
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims description 75
- 239000003054 catalyst Substances 0.000 claims description 68
- 239000010410 layer Substances 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
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- 238000010849 ion bombardment Methods 0.000 claims description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
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- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The application relates to the technical field of electrolyzed water, in particular to a gas diffusion layer with a pore structure, wherein an oxide coating is arranged on a metal substrate by adopting a PVD physical vapor deposition method, the coating on the metal substrate is more uniform, and the gas diffusion layer is particularly suitable for obtaining uniform coating deposition on the metal substrate with the pore structure, on the front and back planes of the substrate and on the side surfaces of fiber wires, and has the advantages of lower contact resistance, higher corrosion resistance and high anodic reaction catalysis capability; meanwhile, the binding force between the coating and the metal substrate is good, the binding force of the coating is superior to that of other film forming modes such as evaporation coating, the consumption of noble metal is less than that of a coating baking method and a water electrolysis method, the coating is 5-10 times better than that of other preparation modes according to the calculation of the attachment amount, the cost is greatly reduced, and the coating has excellent catalytic performance. Meanwhile, the vacuum environment prevents oxidation of the metal substrate possibly occurring in the atmosphere in the preparation process from causing the rise of the bulk resistance, and the conductivity is more excellent.
Description
Technical Field
The application relates to the technical field of electrolyzed water, in particular to a gas diffusion layer with a pore structure, a surface modification method and application.
Background
The hydrogen is used as a new generation sustainable new energy, the electric energy conversion rate is up to 60% -80%, and the hydrogen can also be used as raw materials of industrial products such as ammonia, methanol, methane and the like, so that the preparation technology of the hydrogen is widely researched by vast researchers. The proton exchange membrane water electrolysis (PEM) technology has the characteristics of no pollution, flexible utilization of various green energy sources, high starting speed, strong current fluctuation adaptability and the like, and becomes one of important preparation methods of hydrogen. The gas diffusion layer is used as one of key parts of a PEM electrolytic cell, titanium is generally used as a first-choice material of the current PEM hydrogen production gas diffusion layer under the condition of industrial production at present, and has stronger corrosion resistance, but oxide generated in the catalytic reaction process has the defects of increased contact resistance between the diffusion layer and a proton membrane, reduced catalytic efficiency and the like, so that the hydrogen production efficiency is reduced, the service life of the electrolytic cell is shortened and the like. Therefore, surface modification of the gas diffusion layer is a technical breakthrough in the field of PEM hydrogen production.
For example, chinese patent CN114000176a discloses a preparation method of a dual-functional electrolytic water catalyst coating, in which a multi-component composite coating material is prepared by using a water electroplating method, but in the preparation process of the method, the concentration of a solution is continuously reduced along with the production process, and the film forming rate is reduced due to the changed concentration, and even the catalytic performance is affected, so that the result is inconsistent with the expectation. As another example, chinese patent CN113279006a discloses a gas diffusion electrode, a preparation method and application thereof, and the gas diffusion layer is prepared by adopting a photochemical reaction method, and although the cost of noble metal is reduced, the cost of metalloporphyrin is far higher than that of noble metal, and the feasibility of mass production is low. And both coating preparation modes are carried out under the atmosphere, and the product substrate is easy to oxidize to reduce the conductivity.
The present application is therefore based on the above-mentioned problems, and improves on the prior art gas diffusion layers and methods of making the same.
Disclosure of Invention
Aiming at the technical problems in the prior art, the application aims to provide a gas diffusion layer with a pore structure, and simultaneously provides a surface modification method and application thereof. The method adopts a vacuum magnetron sputtering method in a PVD physical vapor deposition method to prepare the low-load catalyst layer with good uniformity, excellent binding force, high corrosion resistance, high conductivity and long service life, and the vacuum environment prevents the increase of the bulk resistance caused by the possible oxidation of the metal substrate in the atmosphere. The preparation mode of the method has repeatability and batchability, and tools and equipment cavities with different specifications can be selected for batch production according to the product size.
In order to achieve the above purpose, the technical scheme provided by the application is as follows:
the application provides a gas diffusion layer with a pore structure, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a substrate with the pore structure, and the catalyst coating comprises, but is not limited to, metals, non-metals, semiconductors, alloys and corresponding oxides or nitrides thereof.
On the basis of the technical scheme, the metal base material is one or more of a titanium fiber sintered felt, a titanium powder sintered felt and a titanium net, and the porosity is more than 70%. More preferably, the metal substrate is a titanium fiber sintered felt with a porosity of 70% and a thickness of 0.25mm.
On the basis of the technical scheme, the source material of the catalyst coating is one or more of Pt, ir, ta, mo, ru, au, cr, sn, W, si and C element.
On the basis of the technical scheme, the deposition thickness of the catalyst coating on the metal substrate is 5-800nm; more preferably, the catalyst coating is deposited on the metal substrate to a thickness of 5 to 300nm.
The application provides a preparation method of a gas diffusion layer with a pore structure, which comprises the following steps: step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure;
step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
According to the application, the PVD physical vapor deposition method is adopted to provide the oxide coating on the metal substrate, so that the coating on the metal substrate is more uniform, and the method is particularly suitable for obtaining uniform coating deposition on the metal substrate with a pore structure, on the front and back planes of the substrate and on the side surfaces of the fiber, and has the advantages of lower contact resistance, higher corrosion resistance and high anodic reaction catalysis capability; meanwhile, the binding force between the coating and the metal substrate is good, the binding force of the coating is superior to that of other film forming modes such as evaporation coating, the consumption of noble metal is less than that of a coating baking method and a water electrolysis method, the coating is 5-10 times better than that of other preparation modes according to the calculation of the attachment amount, the cost is greatly reduced, and the coating has excellent catalytic performance. Meanwhile, the vacuum environment prevents oxidation of the metal substrate possibly occurring in the atmosphere in the preparation process from causing the rise of the bulk resistance, and the conductivity is more excellent. The preparation mode of the method has repeatability and batchability, and tools and equipment cavities with different specifications can be selected for batch production according to the product size.
Meanwhile, the PVD physical vapor deposition method is adopted to prepare the catalyst coating, so that compared with an evaporation type coating method, the catalyst coating has better binding force between the coating and a base material and better uniformity; compared with chemical vapor deposition, the temperature of the metal substrate can be increased along with the increase of the reaction time in the process of reaction film formation, so that the reaction heat of the metal substrate in the process of film formation and coating is reduced, and the metal substrate has a higher deposition rate than that of chemical vapor deposition; compared with the traditional wet plating such as water plating, the method has no pollution to the environment.
In addition, the source material of the catalyst coating can be more selective, namely, metal, nonmetal, semiconductor material, alloy and the like can be used as target elements of the catalyst coating.
On the basis of the technical scheme, the cleaning in the first step comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 0.1-5mol/L, wherein the cleaning frequency is 5-40KHZ, and the cleaning time is 100-600S; preferably, the concentration of the sulfuric acid is 0.5-2mol/L, the cleaning frequency is 20-40KHZ, and the cleaning time is 300-600s;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 0.1-5mol/L, rinsing for a plurality of times by using deionized water, and drying by using a drying box after rinsing; preferably, the concentration of the NaOH alkaline solution is 0.5-2mol/L; the ultrasonic frequency is selected to be 20KHZ, and the ultrasonic time is 300S.
S3, ultrasonically cleaning the metal substrate obtained in the step S2 by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 5-40KHZ, and the ultrasonic time is 10-300S. Preferably, the ultrasonic frequency is 10-30KHZ, and the ultrasonic time is 150-300s.
The cleaning process in the first step has the effects of removing impurities on one hand and preventing the adverse effect of pollutants on the subsequent coating, wherein the acid can wash away the attached oxide, and the hydrocarbon cleaning agent can clean and degreasing and remove organic matters; on the other hand, more importantly, the adhesive force and the adhesive quantity in the deposition process can be increased, and the surface of the cleaned substrate is easier to adhere and has good adhesive force. Therefore, the surface of the cleaned substrate can form an uneven structure, more attachment sites are provided for the attachment of the plating layer, a plating layer structure with stronger binding force is formed, and the catalytic efficiency is improved.
On the basis of the technical scheme, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves; simultaneously vacuuming the interior of the equipment to a vacuum degree of 1.0 x 10 -4 To 1pa; preferably, the vacuum degree in the magnetron sputtering device is 4.0×10 -2 -1pa；
Compared with the static PVD coating deposition in the prior art, the magnetron sputtering equipment has better permeation effect, the coating is deposited on the outer surface of the base material, and the coating is deposited on the side surface of the fiber yarn, so that the coating is more uniform in coating application, good in binding force, high in catalytic efficiency and good in corrosion resistance.
S5, heating after the vacuum degree in the step S4 reaches a preset value, introducing 10-300sccm argon, opening an ion source to perform ion bombardment cleaning, controlling the bombardment energy to be 20-200eV, cleaning for 100-1000S, and heating to 100-500 ℃ to enable the vacuum degree to reach 1.0 x 10 required by sputtering -3 To 1pa; preferably, the heating temperature is 150-300 ℃, the argon flux is 20-80sccm, the bombardment energy is 60-90eV, and the cleaning time is 300-800s;
the method is characterized in that cleaning is further carried out before film formation by deposition, and impurities possibly attached and oxides possibly generated in the atmospheric environment after the cleaning in the first step and before film formation are removed by adopting an ion bombardment cleaning mode, and atomic vacancies are generated by bombarding atoms of a substrate, so that film layer atoms are more beneficial to film formation by deposition on the substrate.
S6, after the cleaning is finished, one or more of 5-300sccm oxygen, argon, hydrogen or nitrogen is/are introduced until the vacuum degree is less than 7.0 x 10 -1 After pa, remain stable; setting sputtering power to be 50-500w, target spacing to be 50-300mm, sputtering catalyst target material for 60-3000s, and depositing an oxidant coating with thickness of 5-800nm, namely a catalyst coating, on the metal substrate; preferably, the gas inlet amount is 40-150sccm, and the vacuum degree is 0.07-0.7pa; wherein sputtering power is the product of target voltage and current; preferably, the target pitch is150-240mm, sputtering time of 100-1000s, and deposition thickness of 20-180nm; the sputtering power is 150-450w.
S7, closing oxygen supply, increasing argon quantity, and charging and taking the workpiece when the furnace temperature is reduced to 40-60 ℃.
On the basis of the technical scheme, the hydrocarbon cleaning agent in the step S3 is one or more of petroleum ether, ethanol, methanol, acetone and diethyl ether, and can also be an alkane mixture containing normal hydrocarbon, heterogeneous hydrocarbon, naphthene, aromatic hydrocarbon and the like.
On the basis of the technical scheme, the rotation direction of the inner rotation and the revolution direction of the magnetron sputtering equipment in the step S4 are opposite, and the revolution frequency of the rotating frame is 30-75hz. More preferably, the revolution frequency is 40 to 70hz. The method has the advantages that the metal substrate to be transferred moves in the magnetron sputtering equipment in a revolution and rotation mode, as shown in fig. 5, the metal substrate is matched with sputtering targets at a plurality of positions on the inner wall of the equipment, and finally, the metal substrate, especially the front side and the back side of the metal substrate with a pore structure, and the side face of the fiber wire can be subjected to coating deposition.
The application also provides application of the gas diffusion layer with the pore structure in water electrolysis of the ion exchange membrane. In particular, the gas diffusion layer used as an electrolytic cell in proton exchange membrane water electrolysis (PEM) technology has excellent corrosion resistance, high hydrogen production efficiency and improved service life of the electrolytic cell.
The technical scheme provided by the application has the beneficial effects that:
1. the application provides a gas diffusion layer with a pore structure, which is used for preparing a low-load catalyst layer with good uniformity, excellent binding force, high corrosion resistance, high conductivity and long service life on a metal substrate, has excellent electrocatalytic performance, is 5-10 times better than other preparation modes according to the calculation of the load, and effectively reduces the cost; meanwhile, the source material of the catalyst coating has stronger selectivity, namely, the source material comprises metal, nonmetal, semiconductor material, alloy and the like, and can be used as a target element of the catalyst coating.
2. The application also provides a surface modification method of the gas diffusion layer, which is characterized in that an oxide coating is arranged on a metal substrate by adopting a PVD physical vapor deposition method, so that the coating on the metal substrate is more uniform, and the method is particularly suitable for obtaining uniform coating deposition on the metal substrate with a pore structure, on the front and back planes of the substrate and on the side surfaces of fiber wires, and has the advantages of lower contact resistance, higher corrosion resistance and high anodic reaction catalysis capability; meanwhile, the binding force between the coating and the metal substrate is good, the binding force of the coating is superior to that of other film forming modes such as evaporation coating, the consumption of noble metal is less than that of a coating baking method and a water electrolysis method, the coating is 5-10 times better than that of other preparation modes according to the calculation of the attachment amount, the cost is greatly reduced, and the coating has excellent catalytic performance. Meanwhile, the vacuum environment prevents oxidation of the metal substrate possibly occurring in the atmosphere in the preparation process from causing the rise of the bulk resistance, and the conductivity is more excellent.
Drawings
FIG. 1 is a voltammogram obtained from the application of the gas diffusion layers of example 1, comparative example 1, and example 4 to a PEM cell in accordance with the present application;
FIG. 2 is a scanning electron microscope image of a gas diffusion layer according to embodiment 1 of the present application;
FIG. 3 is a scanning electron microscope image of a gas diffusion layer of comparative example 1 of the present application;
FIG. 4 is a scanning electron microscope image of a gas diffusion layer according to embodiment 4 of the present application;
FIG. 5 is a schematic view of the structure of the revolution and rotation turret according to the present application;
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical solutions of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items. It is to be understood that various raw materials in the present application are commercially available unless otherwise specified.
Example 1
The embodiment provides a gas diffusion layer, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a titanium fiber sintered felt substrate with a pore structure, the area is 30 x 30cm, the area is 0.25mm, and the porosity is 70%; the catalyst coating is an oxide of metallic iridium.
In this embodiment, a method for preparing a gas diffusion layer is provided, including the following steps:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure; specifically, the cleaning comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 0.5mol/L, wherein the cleaning frequency is 20KHZ, and the cleaning time is 300S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 1mol/L, and then rinsing for multiple times by deionized water, wherein the ultrasonic frequency is selected to be 20KHZ, and the ultrasonic time is 300S; ensuring no ion residue, rinsing, drying at 60deg.C for 15min, and removing water;
and S3, placing the dried titanium fiber sintered felt in a vacuum hydrocarbon cleaning machine for ultrasonic cleaning, and cleaning by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 10KHZ, and the ultrasonic time is 200S.
Step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
Specifically, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves at the rotating speed of 40hz; simultaneously vacuuming the interior of the equipment to a vacuum degree of 1.0 x 10 -2 pa；
S5, heating the workpiece after the vacuum degree in the step S4 reaches a preset value, heating the workpiece to 150 ℃, introducing 80sccm argon, opening an ion source to perform ion bombardment cleaning, wherein the bombardment energy is controlled at 60eV, and the cleaning time is 300S;
s6, after the cleaning is finished, introducing oxygen with the concentration of 40sccm, and when the vacuum degree reaches 1.0 x 10 -1 After pa, remain stable; setting sputtering power to 150w, target spacing to 150mm, sputtering catalyst target for 100s, and depositing an oxidant coating with thickness of 20nm, namely a catalyst coating, on the metal substrate;
s7, closing oxygen supply, and increasing argon quantity until the furnace temperature is reduced to 40 ℃.
Example 2
The embodiment provides a gas diffusion layer, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a titanium fiber sintered felt substrate with a pore structure, the area is 30 x 30cm, the area is 0.25mm, and the porosity is 70%; the catalyst coating is an oxide of metallic tantalum.
In this embodiment, a method for preparing a gas diffusion layer is provided, including the following steps:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure; specifically, the cleaning comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 0.5mol/L, wherein the cleaning frequency is 20KHZ, and the cleaning time is 300S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 0.5mol/L, and then rinsing for multiple times by using deionized water, wherein the ultrasonic frequency is selected to be 30KHZ, and the ultrasonic time is 300S; ensuring no ion residue, rinsing, drying at 60deg.C for 15min, and removing water;
and S3, placing the dried titanium fiber sintered felt in a vacuum hydrocarbon cleaning machine for ultrasonic cleaning, and cleaning by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 30KHZ, and the ultrasonic time is 300S.
Step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
Specifically, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves at the rotating speed of 70hz; simultaneously vacuuming the interior of the equipment to a vacuum degree of 1.0 x 10 -1 pa；
S5, heating the workpiece after the vacuum degree in the step S4 reaches a preset value, heating the workpiece to 300 ℃, introducing 20sccm of oxygen, opening an ion source to perform ion bombardment cleaning, wherein the bombardment energy is controlled to be 90eV, and the cleaning time is 300S;
s6, after the cleaning is finished, introducing 5-300sccm of oxygen, nitrogen or hydrogen until the vacuum degree reaches 7.0 x 10 - 1 After pa, remain stable; setting sputtering power to 450w, setting target spacing to 240mm, sputtering catalyst target for 800s, and depositing an oxidant coating with thickness of 180nm, namely a catalyst coating, on the metal substrate;
s7, closing oxygen supply, and increasing argon quantity until the furnace temperature is reduced to 40 ℃.
Example 3
The embodiment provides a gas diffusion layer, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a titanium fiber sintered felt substrate with a pore structure, the area is 30 x 30cm, the area is 0.25mm, and the porosity is 70%; the catalyst coating is an oxide of metallic tungsten.
In this embodiment, a method for preparing a gas diffusion layer is provided, including the following steps:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure; specifically, the cleaning comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 1mol/L, wherein the cleaning frequency is 30KHZ, and the cleaning time is 300S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 2mol/L, and then rinsing for multiple times by deionized water, wherein the ultrasonic frequency is selected to be 28KHZ, and the ultrasonic time is 300S; ensuring no ion residue, rinsing, drying at 60deg.C for 15min, and removing water;
and S3, placing the dried titanium fiber sintered felt in a vacuum hydrocarbon cleaning machine for ultrasonic cleaning, and cleaning by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 28KHZ, and the ultrasonic time is 500S.
Step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
Specifically, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves at the rotating speed of 60hz; simultaneously vacuumizing the inside of the equipment, wherein the vacuum degree is less than 1.0 x 10 < -3 > Pa;
s5, heating the workpiece after the vacuum degree in the step S4 reaches a preset value, heating the workpiece to 200 ℃, introducing 60sccm argon, opening an ion source to perform ion bombardment cleaning, wherein the bombardment energy is controlled at 70eV, and the cleaning time is 500S;
s6, after the cleaning is finished, 80sccm of oxygen is introduced until the vacuum degree reaches 1.0 x 10 -1 After pa, remain stable; setting sputtering power to 200w, target spacing to 200mm, sputtering catalyst target for 500s, and depositing an oxidant coating with thickness of 130nm, namely a catalyst coating, on the metal substrate;
s7, closing oxygen supply, and increasing argon quantity until the furnace temperature is reduced to 40 ℃.
Example 4
The embodiment provides a gas diffusion layer, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a titanium fiber sintered felt substrate with a pore structure, the area is 30 x 30cm, the area is 0.25mm, and the porosity is 70%; the catalyst coating is a nitride of metallic titanium.
In this embodiment, a method for preparing a gas diffusion layer is provided, including the following steps:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure; specifically, the cleaning comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 1mol/L, wherein the cleaning frequency is 30KHZ, and the cleaning time is 300S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 2mol/L, and then rinsing for multiple times by deionized water, wherein the ultrasonic frequency is selected to be 28KHZ, and the ultrasonic time is 300S; ensuring no ion residue, rinsing, drying at 60deg.C for 15min, and removing water;
and S3, placing the dried titanium fiber sintered felt in a vacuum hydrocarbon cleaning machine for ultrasonic cleaning, and cleaning by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 28KHZ, and the ultrasonic time is 500S.
Step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
Specifically, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves at the rotating speed of 60hz; simultaneously vacuumizing the inside of the equipment, wherein the vacuum degree is less than 1.0 x 10 < -3 > Pa;
s5, heating the workpiece after the vacuum degree in the step S4 reaches a preset value, heating the workpiece to 200 ℃, introducing 60sccm argon, opening an ion source to perform ion bombardment cleaning, wherein the bombardment energy is controlled at 70eV, and the cleaning time is 500S;
s6, after the cleaning is finished, 80sccm of nitrogen is introduced until the vacuum degree reaches 1.0 x 10 -1 After pa, remain stable; setting sputtering power to 200w, target spacing to 200mm, sputtering catalyst target for 500s, and depositing a nitride coating with thickness of 110nm, namely a catalyst coating, on the metal substrate;
s7, closing the nitrogen supply, and increasing the argon quantity until the furnace temperature is reduced to 40 ℃.
Comparative example 1
The embodiment provides a gas diffusion layer, which comprises a metal substrate and a catalyst coating, wherein the metal substrate is a titanium fiber sintered felt substrate with a pore structure, the area is 30 x 30cm, the area is 0.25mm, and the porosity is 70%; the catalyst coating is an oxide of metallic iridium.
In this embodiment, a method for preparing a gas diffusion layer is provided, including the following steps:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure; specifically, the cleaning comprises the following steps:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 0.5mol/L, wherein the cleaning frequency is 20KHZ, and the cleaning time is 30S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 1mol/L, and then rinsing for multiple times by deionized water, wherein the ultrasonic frequency is selected to be 20KHZ, and the ultrasonic time is 300S; ensuring no ion residue, rinsing, drying at 60deg.C for 15min, and removing water;
and S3, placing the dried titanium fiber sintered felt in a vacuum hydrocarbon cleaning machine for ultrasonic cleaning, and cleaning by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 10KHZ, and the ultrasonic time is 200S.
Step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
Specifically, the preparation of the catalyst coating in the second step comprises the following steps:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein the device adopts a conventional coating process, a public self-transmission tool frame is not arranged, and a mode that the front face faces the target material for sputtering is adopted, which is different from that in the embodiment 1; simultaneously vacuuming the interior of the equipment to a vacuum degree of 1.0 x 10 -2 pa；
S5, heating the workpiece after the vacuum degree in the step S4 reaches a preset value, heating the workpiece to 150 ℃, introducing 80sccm argon, opening an ion source to perform ion bombardment cleaning, wherein the bombardment energy is controlled at 60eV, and the cleaning time is 300S;
s6, after the cleaning is finished, introducing oxygen with the concentration of 40sccm, and when the vacuum degree reaches 1.0 x 10 -1 After pa, remain stable; setting sputtering power to 150w, target spacing to 150mm, sputtering catalyst target for 100s, and depositing an oxidant coating with thickness of 30nm, namely a catalyst coating, on the metal substrate;
s7, closing oxygen supply, increasing argon volume, and finishing one side coating of the substrate when the furnace temperature is reduced to 40 ℃;
s8, after the workpiece is taken out, replacing the other surface of the base material, and carrying out surface punching on the target material to repeat the S4-S7 process, thereby completing the coating on the two surfaces of the base material.
As shown in fig. 1 to 4, the gas diffusion layers of example 1, comparative example 1 and example 4 were applied to PEM cells as voltammograms obtained by anode gas diffusion layer testing; from voltammogram analysis, according to the results of the performance test of the gas diffusion layer prepared in example 1 and the gas diffusion layer prepared in comparative example 1, the thickness of the catalyst coating layer in comparative example 1 was 10nm thicker than that in example 1 in the case of the same substrate and catalyst raw materials, but the catalytic performance was not comparable to that in example 1, mainly because the gas diffusion layer in example 1 was coated by the revolution/rotation coordination method to be protected in the present application, the catalyst coating layer was provided on the surface of the substrate and the side surface of the substrate, the coating layer was more uniform, the specific surface area was larger, and the catalytic activity was better, and the scanning electron microscope images of the gas diffusion layers in fig. 2 and 3 were seen specifically. It can also be seen that the catalytic activity in example 4 is close to that of comparative example 1 and does not differ much from that of example 1, specifically, at the same current density, i.e., 2.0A, the voltage values corresponding to example 1, comparative example 1 and example 4 are 1.82V, 1.85V and 1.86V, respectively; since the non-noble metal nitride is used for the catalyst coating in example 4, the method for preparing the gas diffusion layer according to the present application is also described, and the catalytic performance of the non-noble metal material can be achieved close to that of the noble metal material, which is closely related to the specific surface area and uniformity of the catalyst coating.
Furthermore, as can be seen from the voltammogram in fig. 1, the conductivity and corrosion resistance in example 1 of the present application are both optimal; the corrosion resistance is related to the curvature of the voltammetric curve, and the smaller the curvature is, the better the corrosion resistance is; the lower the voltage, the better its conductivity at the same current.
While the fundamental and principal features of the application and advantages of the application have been shown and described, it will be apparent to those skilled in the art that the application is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A gas diffusion layer having a pore structure, comprising a metal substrate and disposed on a catalyst coating, wherein the metal substrate is a substrate having a pore structure, and the catalyst coating comprises, but is not limited to, a metal, a nonmetal, a semiconductor, an alloy, and their corresponding oxides or nitrides.
2. The gas diffusion layer with a pore structure according to claim 1, wherein the metal substrate is one or more of a titanium fiber sintered felt, a titanium powder sintered felt, and a titanium mesh, and the porosity is 70% or more.
3. A gas diffusion layer having a pore structure according to claim 1, wherein the source material of the catalyst coating is one or more of Pt, ir, ta, mo, ru, au, cr, sn, W, si and element C.
4. A gas diffusion layer having a pore structure according to claim 1, wherein the catalyst coating is deposited on the metal substrate to a thickness of 5-800nm.
5. A method for modifying the surface of a gas diffusion layer having a pore structure according to any one of claims 1 to 4, comprising the steps of:
step one, pretreatment of a metal substrate: cleaning the surface of the metal substrate and the side wall of the pore structure;
step two, preparing a catalyst coating: based on the physical vapor deposition PVD method principle, an unbalanced magnetron sputtering device is adopted to prepare a layer of oxide coating, namely a catalyst coating, on a metal substrate.
6. The method for modifying the surface of a gas diffusion layer having a pore structure according to claim 5, wherein the cleaning in the first step comprises the steps of:
s1, cleaning a metal substrate by using sulfuric acid with the concentration of 0.1-5mol/L, wherein the cleaning frequency is 5-40KHZ, and the cleaning time is 100-600S;
s2, neutralizing the metal substrate obtained in the step S1 by adopting NaOH alkaline solution with the concentration of 0.1-5mol/L, rinsing for a plurality of times by using deionized water, and drying by using a drying box after rinsing;
s3, ultrasonically cleaning the metal substrate obtained in the step S2 by using a hydrocarbon cleaning agent, wherein the ultrasonic frequency is 5-40KHZ, and the ultrasonic time is 10-300S.
7. The method for modifying the surface of a gas diffusion layer having a pore structure according to claim 5, wherein the catalyst coating layer preparation in the step two comprises the steps of:
s4, placing the pretreated metal substrate in a magnetron sputtering device, wherein a revolution and rotation rotating frame is arranged in the device, the metal substrate is fixed on a clamp to rotate, and then the rotating frame revolves; simultaneously vacuuming the interior of the equipment to a vacuum degree of 1.0 x 10 -4 To 1pa;
s5, heating after the vacuum degree in the step S4 reaches a preset value, introducing 10-300sccm argon, opening an ion source to perform ion bombardment cleaning, controlling the bombardment energy to be 20-200eV, cleaning for 100-1000S, and heating to 100-500 ℃ to enable the vacuum degree to reach 1.0 x 10 required by sputtering -3 To 1pa;
s6, after the cleaning is finished, one or more of 5-300sccm oxygen, argon, hydrogen or nitrogen is/are introduced until the vacuum degree is less than 7.0 x 10 -1 After pa, remain stable; setting sputtering power to be 50-500w, target spacing to be 50-300mm, sputtering catalyst target material for 60-3000s, and depositing an oxidant coating with thickness of 5-800nm, namely a catalyst coating, on the metal substrate;
s7, closing oxygen supply, and increasing argon quantity until the furnace temperature is reduced to 40-60 ℃.
8. The method for surface modification of porous gas diffusion layer according to claim 6, wherein the hydrocarbon cleaning agent in step S3 is one or more of petroleum ether, ethanol, methanol, acetone, and diethyl ether.
9. The method for modifying the surface of a gas diffusion layer having a pore structure according to claim 7, wherein the rotation direction of the rotation and the revolution in the magnetron sputtering apparatus in the step S4 are opposite, and the revolution frequency of the turret is 30 to 75hz.
10. Use of a gas diffusion layer having a pore structure according to claim 1 in the electrolysis of water by an ion exchange membrane.
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