CN218089828U - Hydrogen production diaphragm and electrolytic cell - Google Patents
Hydrogen production diaphragm and electrolytic cell Download PDFInfo
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- CN218089828U CN218089828U CN202222289831.8U CN202222289831U CN218089828U CN 218089828 U CN218089828 U CN 218089828U CN 202222289831 U CN202222289831 U CN 202222289831U CN 218089828 U CN218089828 U CN 218089828U
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 62
- 239000010410 layer Substances 0.000 claims abstract description 270
- 239000002105 nanoparticle Substances 0.000 claims abstract description 62
- 239000011241 protective layer Substances 0.000 claims abstract description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 58
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- 239000012528 membrane Substances 0.000 claims abstract description 19
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- -1 hydroxyl compound Chemical class 0.000 claims description 20
- 238000005868 electrolysis reaction Methods 0.000 abstract description 17
- 239000013535 sea water Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
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Images
Classifications
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- 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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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The utility model provides a hydrogen production diaphragm and an electrolytic cell, wherein the hydrogen production diaphragm comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer. The hydrogen production diaphragm has higher stability and lower resistance, is beneficial to the generation of oxygen evolution reaction in seawater, and improves the hydrogen production activity by electrolysis. The hydrogen production membrane comprises a regular pore channel structure of the MOF nano particles, and is favorable for realizing high current density. The electrolytic cell made of the hydrogen production diaphragm can realize low-cost, flexible and efficient renewable energy source green hydrogen preparation.
Description
Technical Field
The utility model belongs to hydrogen energy and sea water resource utilization field, concretely relates to hydrogen production diaphragm and electrolysis trough.
Background
The hydrogen production by alkaline electrolysis of water has the advantages of large hydrogen production capacity of monomer equipment and low cost, and is the mainstream technical choice for realizing large-scale green hydrogen production at present. However, the mainstream hydrogen production technology by water electrolysis has higher requirements on the water quality of raw water, even in areas with rich water resources, the raw water is often applied by a purifying party, the hydrogen production process by water electrolysis is complicated, the cost is high, and the development of the hydrogen production technology by water electrolysis in different areas is limited.
The reserves of seawater on the earth are very rich, and resources such as offshore wind energy, solar energy, wave energy and the like are rich, and the direct electrolytic hydrogen production by utilizing the seawater is favorable for the popularization of green hydrogen production. However, the high content of chloride ions in seawater causes corrosion and damage to the materials of the electrolytic hydrogen production system, and the oxidation of chloride ions competes for the oxygen evolution reaction of the electrolytic hydrogen production.
SUMMERY OF THE UTILITY MODEL
In view of this, the present invention provides a hydrogen production diaphragm and an electrolytic cell, which are beneficial to improving the hydrogen production activity by electrolysis.
In order to achieve the purpose, the technical scheme of the utility model is a hydrogen production diaphragm, which comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chlorine ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chlorine ion barrier layer.
In the hydrogen production diaphragm, the hydrogen production diaphragm also comprises an MOF nano particle layer arranged between the body layer and the protective layer.
In the hydrogen production diaphragm, the thickness of the body layer is 100-300 μm, the thickness of the protective layer is 0.4-4 μm, the thickness of the alkaline modification layer is 0.2-2 μm, and the thickness of the chloride ion barrier layer is 0.2-2 μm.
In the hydrogen production diaphragm, the body layer is the engineering plastic layer of reinforcing, basicity modification layer is the hydroxyl compound layer, and the chloride ion barrier layer is the sulfonic acid compound layer.
The utility model provides a hydrogen manufacturing diaphragm has high stability and lower resistance, is favorable to reducing electrolysis cell volume, can effectively block chloride ion, forms local alkaline environment on the diaphragm surface to do benefit to the emergence of the oxygen evolution reaction in the sea water. The hydrogen production membrane has a regular pore channel structure of the MOF nano particles, enhances the gas permeability of the membrane, and can promote the rapid separation of gas under high current density, thereby being beneficial to realizing the high current density. The diaphragm is provided with an alkaline modification layer, so that a local alkaline environment can be created on the surface, and the improvement of the selectivity of the oxygen evolution reaction in the presence of chloride ions in seawater is facilitated. Meanwhile, the diaphragm is provided with a chloride ion barrier layer, so that chloride ions can be effectively rejected, the adverse effect of the chloride ions on the anion conduction effect is avoided, the corrosion of the chloride ions on the diaphragm is effectively prevented, the service life of the diaphragm is prolonged, and the diaphragm can be used for directly electrolyzing seawater to prepare hydrogen.
The utility model also provides an electrolytic cell, include: the hydrogen production diaphragm comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer.
In the electrolytic cell, the utility model also comprises an MOF nano-particle layer arranged between the body layer and the protective layer.
In the electrolytic bath, the thickness of the body layer is 100 to 300 mu m, the thickness of the protective layer is 0.4 to 4 mu m, the thickness of the alkaline modification layer is 0.2 to 2 mu m, and the thickness of the chloride ion barrier layer is 0.2 to 2 mu m.
In the electrolytic cell, the body layer is an enhanced engineering plastic layer, the alkaline modification layer is a hydroxyl compound layer, and the chloride ion barrier layer is a sulfonic acid compound layer.
The utility model provides an electrolysis trough can realize low-cost, nimble efficient green hydrogen preparation of renewable energy, and the diaphragm in the electrolysis trough has high stability and lower resistance, is favorable to reducing electrolysis cell volume, can effectively block chloride ion, forms local alkaline environment on the diaphragm surface to do benefit to the emergence of oxygen evolution reaction in the sea water. The hydrogen production diaphragm can promote the rapid separation of gas under high current density, thereby being beneficial to realizing high current density.
The utility model provides a hydrogen production diaphragm, which comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chlorine ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chlorine ion barrier layer. The hydrogen production diaphragm has high stability and low resistance, is beneficial to reducing the volume of an electrolysis small chamber, can effectively block chloride ions, can keep voltage stable in a high-chloride-ion environment, and forms a local alkaline environment on the surface of the diaphragm, so that the generation of oxygen evolution reaction in seawater is facilitated, the hydrogen production activity of electrolysis is improved, the corrosion of the chloride ions to the hydrogen production diaphragm is prevented, and the service life of the diaphragm is prolonged. The hydrogen production diaphragm can promote the rapid separation of gas under high current density, thereby being beneficial to realizing high current density. The electrolytic cell made of the hydrogen production diaphragm can realize the low-cost, flexible and efficient renewable energy source green hydrogen preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a hydrogen production membrane;
FIG. 2 is a schematic diagram of an alkaline zero-spacing electrolyzer.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
The hydrogen production diaphragm provided by the utility model comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer.
Referring to fig. 1, fig. 1 is a schematic view of a hydrogen production diaphragm, which includes a body layer 1.1, an alkaline modification layer 1.2 compounded on the surface of the body layer, and a chloride ion blocking layer 1.3 compounded on the surface of the alkaline modification layer. Or the hydrogen production diaphragm comprises a body layer 1.1, a chloride ion barrier layer 1.2 compounded on the surface of the body layer and an alkaline modification layer 1.3 compounded on the surface of the chloride ion barrier layer.
In the hydrogen production diaphragm of the utility model, the thickness of the body layer is 100-300 μm, preferably 50-200 μm. The body layer is a reinforced engineering plastic layer which can be commercially available, such as a polysulfone/polyphenylene sulfide layer, and can also be prepared by mixing engineering plastics and reinforcing agents, wherein the engineering plastics comprise polyphenylene sulfide and polyether ether ketone, and the reinforcing agents comprise polysulfone and polyvinylpyrrolidone. The preparation method of the body layer can be as follows: mixing engineering plastics and reinforcing agent, and forming the body layer by adopting a thermoforming and tape casting method. The tape casting method comprises the steps of dissolving engineering plastics and a reinforcing agent in a solvent, scraping the solution on a flat glass plate by adopting a scraper, adjusting the thickness of a body layer by changing the height of the scraper relative to the glass plate, and volatilizing the solvent to obtain the body layer.
The body layer can also include MOF nano-particles, and the body layer is the engineering plastics and the MOF nano-particles composite bed of reinforcing, the engineering plastics of reinforcing can include engineering plastics and reinforcing agent, the body layer can be prepared through following method and obtain: will projectAnd (2) mixing and dissolving plastic, reinforcing agent and MOF nano particles in a solvent, wherein the mass ratio of the reinforcing agent to the MOF nano particles is 10-30 6 O 4 (OH) 4 -trimesic acid or MOF-801, using thermoforming and tape casting, scraping the solution onto a flat glass plate using a doctor blade, adjusting the thickness of the bulk layer by varying the height of the doctor blade relative to the glass plate, volatilizing the solvent to obtain the bulk layer; or mixing and dissolving the MOF nano particles and the reinforcing agent to obtain a coating material solution, compounding the coating material solution on a support body formed by engineering plastics by adopting a thermal forming and tape casting method and adopting a scraper, and volatilizing the solvent by changing the height of the scraper relative to the support body to adjust the thickness of the body layer to form the body layer. The reinforcing agent and metal elements of the MOF nano particles form hydrogen bonds, so that the stability of the diaphragm is enhanced, the thickness of the diaphragm can be reduced, the surface resistance is reduced, and the hydrogen production efficiency by electrolysis is improved.
In the hydrogen production diaphragm of the utility model, the protective layer has a thickness of 0.4 to 4 μm and comprises a hydroxyl compound and a sulfonic acid compound composite layer. The protective layer may be formed on the surface of the bulk layer by commercially available polyvinyl alcohol/Nafion composite layers, for example, and also by the following method: the protective layer is formed on the surface of the body layer in a spin coating and in-situ growth mode, wherein the in-situ growth mode is specifically that the protective layer is grafted, polymerized, singly loaded and deposited on the body layer by an electrochemical or physical method to obtain the protective layer in-situ growth on the body layer.
In one embodiment, the protective layer of the present invention comprises an alkaline modification layer compounded on the bulk layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer. The alkaline modification layer is a hydroxyl compound layer, can be an alcohol polymer layer and has the thickness of 0.2-2 mu m; in one embodiment, the alkaline modifying layer is a polyvinyl alcohol layer; the alkaline modification layer can be commercially available, such as a polyvinyl alcohol layer, and can also be formed on the surface of the bulk layer or the chlorine ion barrier layer by in-situ growth, coating or drop casting. The chloride ion barrier layer is a sulfonic acid compound layer, can be a Nafion layer or a sulfonated UIO-66 metal organic framework material layer, has the thickness of 0.2-2 mu m, can be commercially available, such as a Nafion layer, and can also be formed on the surface of the body layer or the alkaline modification layer in an in-situ growing, coating or drop casting mode.
The protective layer of the present invention can further include MOF nanoparticles, and in one embodiment, the protective layer includes hydroxylated MOF nanoparticles and sulfonic acid compound composite layer, which can be obtained by market, for example, hydroxylated MOF nanoparticles/Nafion layer, and also can be obtained by compounding hydroxylated MOF nanoparticles and sulfonic acid compound, and the hydroxylated MOF nanoparticles can be obtained by market, and also can be obtained by hydroxylating MOF nanoparticles by inorganic chemical reduction method or organic small molecule in-situ grafting method. In one embodiment, the protective layer comprises a composite layer of sulfonated MOF nanoparticles and hydroxyl compounds, and can be obtained from the market, for example, sulfonated MOF nanoparticles/polyvinyl alcohol layer, or sulfonated MOF nanoparticles and hydroxyl compounds can be obtained by combining them, and the sulfonated MOF nanoparticles can be obtained from the market, or can be obtained by sulfonating MOF nanoparticles by inorganic chemical reduction or in-situ grafting of small organic molecules.
In one embodiment, the hydrogen production membrane further comprises a layer of MOF nanoparticles disposed between the bulk layer and the protective layer. The MOF nano particle layer can be formed on the surface of the body layer in an electrochemical mode, and a protective layer is formed on the surface of the MOF nano particle layer in-situ growth, coating and drop casting modes. The MOF nano particles are enriched on the surface of the membrane, and larger surface roughness and lower surface layer solid proportion can be constructed, so that the easiness of bubble detachment is improved.
In one embodiment, the contact angle of the bubbles of the diaphragm is 153 degrees, which can ensure that the bubbles formed under a large current density can be quickly separated.
Membrane electrode is constituteed with gas diffusion layer, catalysis layer to diaphragm accessible conventional method, and then forms alkaline zero-spacing electrolysis trough with the assembly of parts such as bipolar plate for the direct electrolytic hydrogen production of sea water realizes low-cost, the green hydrogen preparation of nimble efficient renewable energy.
The utility model also provides an electrolysis trough, include: the hydrogen production diaphragm comprises a body layer and a protective layer on the surface of the body layer; the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer.
The electrolytic bath of the utility model can be an alkaline zero-spacing electrolytic bath, see figure 2, and figure 2 is a structural schematic diagram of the alkaline zero-spacing electrolytic bath, which comprises a cathode 2, a hydrogen production diaphragm 1 and an anode 3.
In the electrolytic cell of the utility model, the thickness of the body layer is 100-300 μm, preferably 50-200 μm. The body layer is a reinforced engineering plastic layer which can be commercially available, such as a polysulfone/polyphenylene sulfide layer, and can also be prepared by mixing engineering plastics and reinforcing agents, wherein the engineering plastics comprise polyphenylene sulfide and polyether ether ketone, and the reinforcing agents comprise polysulfone and polyvinylpyrrolidone. The preparation method of the body layer can be as follows: mixing engineering plastics and reinforcing agent, and forming the body layer by adopting a thermoforming and tape casting method. The casting method comprises the steps of dissolving engineering plastics and a reinforcing agent in a solvent, scraping the solution on a flat glass plate by adopting a scraper, adjusting the thickness of a body layer by changing the height of the scraper relative to the glass plate, and volatilizing the solvent to obtain the body layer.
In the electrolytic cell, the body layer can also comprise MOF nanoparticles, the body layer is a reinforced engineering plastic and MOF nanoparticle composite layer, the reinforced engineering plastic can comprise engineering plastic and a reinforcing agent, and the body layer can be prepared by the following method: mixing and dissolving engineering plastics, reinforcing agent and MOF nanoparticles in a solvent, wherein the reinforcing agent is prepared by mixing and dissolving the engineering plastics, the reinforcing agent and the MOF nanoparticles in the solventThe mass ratio of the reinforcing agent to the MOF nanoparticles is 10-30, the ratio of the mass sum of the reinforcing agent and the MOF nanoparticles to the mass of the engineering plastic is 5 6 O 4 (OH) 4 -trimesic acid or MOF-801, thermoforming and tape casting, scraping the solution onto a flat glass plate with a doctor blade, adjusting the thickness of the bulk layer by varying the height of the doctor blade relative to the glass plate, volatilizing the solvent to obtain the bulk layer; or mixing and dissolving the MOF nano-particles and the reinforcing agent to obtain a coating material solution, compounding the coating material solution on a support body formed by engineering plastics by adopting a thermal forming and tape casting method and adopting a scraper, and volatilizing the solvent to form the body layer by changing the thickness of the body layer relative to the height of the scraper. The reinforcing agent and metal elements of the MOF nano particles form hydrogen bonds, so that the stability of the diaphragm is enhanced, the thickness of the diaphragm can be reduced, the surface resistance is reduced, and the hydrogen production efficiency by electrolysis is improved.
In the electrolytic cell, the thickness of the protective layer is 0.4-4 μm, and the protective layer comprises a hydroxyl compound and a sulfonic acid compound composite layer. The protective layer may be formed on the surface of the bulk layer by commercially available, for example, polyvinyl alcohol/Nafion composite layers, and also by the following method: the protective layer is formed on the surface of the body layer in a spin coating and in-situ growth mode, and the in-situ growth mode is specifically that the protective layer is grafted, polymerized, singly loaded and deposited on the body layer by an electrochemical or physical method to obtain the protective layer in-situ growth on the body layer.
In one embodiment, the protective layer of the present invention comprises an alkaline modification layer compounded on the bulk layer and a chloride ion barrier layer compounded on the alkaline modification layer; or the protective layer comprises a chlorine ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chlorine ion barrier layer. The alkaline modification layer is a hydroxyl compound layer, can be an alcohol polymer layer and has the thickness of 0.2-2 mu m; in one embodiment, the alkaline modifying layer is a polyvinyl alcohol layer; the alkaline modification layer can be commercially available, such as a polyvinyl alcohol layer, and can also be formed on the surface of the body layer or the chloride ion barrier layer by in-situ growth, coating or drop casting. The chloride ion barrier layer is a sulfonic acid compound layer, can be a Nafion layer or a sulfonated UIO-66 metal organic framework material layer, has the thickness of 0.2-2 mu m, can be commercially available, such as a Nafion layer, and can also be formed on the surface of the body layer or the alkaline modification layer in an in-situ growing, coating or drop casting mode.
In the electrolytic cell, the protective layer can also include MOF nanoparticles, and in one embodiment, the protective layer includes hydroxylated MOF nanoparticles and sulfonic acid compound composite layer, and can be purchased through the market, for example, hydroxylated MOF nanoparticles/Nafion layer, also can be obtained with hydroxylated MOF nanoparticles and sulfonic acid compound complex, hydroxylated MOF nanoparticles can be purchased for the market, also can adopt inorganic chemical reduction method or organic small molecule in situ grafting method to obtain MOF nanoparticles hydroxylation. In one embodiment, the protective layer comprises a composite layer of sulfonated MOF nanoparticles and hydroxyl compounds, and can be obtained from the market, for example, sulfonated MOF nanoparticles/polyvinyl alcohol layer, or sulfonated MOF nanoparticles and hydroxyl compounds can be obtained by combining them, and the sulfonated MOF nanoparticles can be obtained from the market, or can be obtained by sulfonating MOF nanoparticles by inorganic chemical reduction or in-situ grafting of small organic molecules.
In one embodiment, the hydrogen production membrane in the electrolytic cell further comprises a layer of MOF nanoparticles disposed between the body layer and the protective layer. The MOF nano particle layer can be formed on the surface of the body layer in an electrochemical mode, and a protective layer is formed on the surface of the MOF nano particle layer in-situ growth, coating and drop casting modes. The MOF nano particles are enriched on the surface of the membrane, and larger surface roughness and lower surface layer solid proportion can be constructed, so that the easiness of bubble detachment is improved.
In one embodiment, the contact angle of the bubbles of the diaphragm is 153 degrees, which can ensure that the bubbles formed under a large current density can be quickly separated.
Example 1:
preparation of Hydrogen production diaphragm
(1) Forming a body layer: polysulfone and MOF nanoparticles (Zr) in a mass ratio of 15 6 O 4 (OH) 4 A trimesic acid repeating structure with a frame window size of about 1nm, which is synthesized by solvothermal, hydrothermal, electrochemical, physical milling, etc., and has a particle size of 30-50 nm) dispersed in DMF (N, N-dimethylformamide) to form a homogeneous mixture, wherein the mass fraction of polysulfone and MOF particles in the DMF mixture is 30%. The mixture was cast into a film on a glass plate, and a 280 μm polyphenylene sulfide sheet was placed in the mixed solution as a support during casting. By varying the height of the doctor blade relative to the glass plate, a film having a thickness of 300 μm was obtained. The obtained film was dried in an oven at 60 ℃ for 6 hours and then dried in a vacuum oven at 100 ℃ for 12 hours. Peeled from the glass plate and washed 3 times with excess deionized water to give a bulk layer 300 μm thick, which was stored in fresh deionized water prior to use.
(2) Forming an alkaline modification layer: PVA (polyvinyl alcohol) is dissolved in a DMF solution to obtain a PVA solution with the mass fraction of 10%. Uniformly spin-coating the PVA solution on the surface of the body layer at the spin speed of 200rpm for 0.5min, and then vacuum-drying at 50 ℃ for 12h to form an alkaline modification layer with the thickness of 0.2 mu m on the surface of the body layer.
(3) Forming a chloride ion barrier layer: nafion (perfluorosulfonic acid ionic membrane) was dissolved in DMF to obtain a Nafion solution with a mass fraction of 30%. And uniformly spin-coating the Nafion solution on the surface of the alkaline modification layer at the spin speed of 200rpm for 3min, and then carrying out vacuum drying at 50 ℃ for 12h to form a chloride ion barrier layer with the thickness of 2 mu m on the surface of the alkaline modification layer, thereby obtaining the hydrogen production diaphragm. The contact angle of the bubbles of the diaphragm is 153 degrees measured by adopting a bubble capturing method, so that the bubbles formed under the high current density can be ensured to be quickly separated.
Example 2:
a bulk layer of a hydrogen-producing membrane was prepared according to the method of example 1, wherein the bulk layer did not include MOF nanoparticles. The forming method of the protective layer comprises the following steps: hydroxylating the MOF nanoparticles by adopting an inorganic chemical reduction method or an organic small molecule in-situ grafting method. The hydroxylated MOF nanoparticles were mixed with Nafion (perfluorosulfonic acid ionic membrane) solution to obtain a mixed solution. And uniformly spin-coating the mixed solution on the surface of the body layer at the spin-coating speed of 200rpm for 3min, and then carrying out vacuum drying at 50 ℃ for 12h to form a protective layer on the surface of the body layer, thus obtaining the hydrogen production diaphragm.
The hydrogen production membrane surface is enriched with MOF nano particles, so that larger surface roughness and lower surface layer solid proportion can be constructed, and the easiness of bubble detachment is improved.
Example 3:
the hydrogen production separator was prepared according to the method of example 2, wherein the method of forming the body layer was: and sulfonating the MOF nano particles by adopting an inorganic chemical reduction method or an organic small molecule in-situ grafting method. The sulfonated MOF nanoparticles were mixed with PVA (polyvinyl alcohol) solution to obtain a mixed solution. And uniformly spin-coating the mixed solution on the surface of the body layer at the spin speed of 200rpm for 3min, and then performing vacuum drying at 50 ℃ for 12h to form a protective layer on the surface of the body layer to obtain the hydrogen production diaphragm.
The hydrogen production membrane is enriched in MOF nanoparticles on the surface, so that larger surface roughness and lower surface layer solid proportion can be constructed, and the easiness of bubble detachment is improved.
Example 4:
a bulk layer of a hydrogen-producing membrane was prepared according to the method of example 1, wherein the bulk layer did not include MOF nanoparticles. An electrochemical method is adopted to directly synthesize the MOF film layer on the surface of the body layer, and the forming method of the protective layer is as follows: and sulfonating the MOF nano particles by adopting an inorganic chemical reduction method or an organic small molecule in-situ grafting method. The sulfonated MOF nanoparticles were mixed with PVA (polyvinyl alcohol) solution to obtain a mixed solution. And uniformly spin-coating the mixed solution on the surface of the MOF film layer at the spin-coating rotation speed of 200rpm for 3min, and then performing vacuum drying at 50 ℃ for 12h to form a protective layer on the surface of the MOF film layer, thereby obtaining the hydrogen production diaphragm.
The hydrogen production membrane is enriched in MOF nanoparticles on the surface, so that larger surface roughness and lower surface layer solid proportion can be constructed, and the easiness of bubble detachment is improved.
The above description of the embodiments is only intended to help understand the method of the present invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, the present invention can be further modified and modified, and such modifications and modifications also fall within the scope of the appended claims.
Claims (10)
1. The hydrogen production membrane is characterized by comprising a body layer and a protective layer on the surface of the body layer;
the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer;
or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer.
2. The hydrogen-producing membrane of claim 1, further comprising a layer of MOF nanoparticles disposed between the bulk layer and the protective layer.
3. The hydrogen-producing separator according to claim 1, wherein the thickness of the bulk layer is 100 to 300 μm, and the thickness of the protective layer is 0.4 to 4 μm.
4. The hydrogen production separator according to claim 1, wherein the thickness of the alkaline modification layer is 0.2 to 2 μm, and the thickness of the chloride ion barrier layer is 0.2 to 2 μm.
5. The hydrogen production membrane of claim 1, wherein the body layer is a reinforced engineering plastic layer, the alkaline modification layer is a hydroxyl compound layer, and the chloride ion barrier layer is a sulfonic acid compound layer.
6. An electrolytic cell, comprising: the hydrogen production diaphragm comprises a body layer and a protective layer on the surface of the body layer;
the protective layer comprises an alkaline modification layer compounded on the body layer and a chloride ion barrier layer compounded on the alkaline modification layer;
or the protective layer comprises a chloride ion barrier layer compounded on the body layer and an alkaline modification layer compounded on the chloride ion barrier layer.
7. The electrolytic cell of claim 6 further comprising a layer of MOF nanoparticles disposed between the bulk layer and the protective layer.
8. The electrolytic cell of claim 6, wherein the bulk layer has a thickness of 100 to 300 μm and the protective layer has a thickness of 0.4 to 4 μm.
9. The electrolytic cell of claim 6, wherein the alkaline modification layer has a thickness of 0.2 to 2 μm and the chloride ion barrier layer has a thickness of 0.2 to 2 μm.
10. The electrolytic cell of claim 6 wherein the body layer is a reinforced engineering plastic layer, the alkaline modification layer is a hydroxyl compound layer, and the chloride barrier layer is a sulfonic acid compound layer.
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