High-efficiency water electrolysis hydrogen production composite diaphragm with multiple gas barrier layers

Abstract

The invention provides an efficient water electrolysis hydrogen production composite diaphragm with multiple gas barrier layers, and relates to the technical field of composite diaphragm preparation. The preparation method of the electrolytic water hydrogen production composite diaphragm comprises the following steps: S1, mixing PVP, PSU and NMP as solvents in a stirring device, adding ZrO2 nano-powder, and uniformly stirring, S2, continuously mixing the obtained slurry until uniform viscosity is achieved, S3, pouring a suspension into a slit formed by a first scraper with first component skin slurry to form a first gas barrier layer, and S4, adding a second component skin slurry into the first gas barrier layer to form a second gas barrier layer. And S4, standing for a period of time to cure the first gas barrier layer. According to the porous diaphragm, the nanoscale dense gas barrier layer is formed through the interval time of multiple times of slurry coating and slurry pre-evaporation, the permeability of gas can be effectively reduced, and the dense gas barrier layer is extremely thin and does not increase ion impedance, so that hydrogen and oxygen crossing can be effectively avoided under the condition that the electrolysis energy consumption is not increased; and the safety of the electrolytic hydrogen production system is improved.

Description

Technical Field

[0001] This invention relates to the field of composite membrane preparation technology, specifically to a high-efficiency composite membrane for hydrogen production via water electrolysis with multiple barrier layers. Background Technology

[0002] An AWE battery consists of an anode (positive electrode), a cathode (negative electrode), and a porous separator. When a voltage is applied under alkaline electrolyte (KOH) conditions, oxygen is produced at the anode and hydrogen at the cathode. The porous separator is used in conjunction with the electrolyte. The pores in the separator facilitate hydroxyl ion conduction; however, gas cross-permeation occurs during high-pressure and differential pressure operation, which is detrimental to hydrogen production efficiency and safety. Therefore, the structure and shape of the pores are key factors determining the separator's performance. An ideal AWE separator should incorporate materials with a porous structure that maintain excellent gas barrier properties while exhibiting low resistance.

[0003] Currently, one of the commercially available separators for AWE is Agfa (Belgium)'s Zirfon, a porous reinforced composite separator made of hydrophilic zirconium oxide nanoparticles, polysulfone (PSU) binder, and polyphenylene sulfide (PPS) carrier, offering mechanical strength. Zircon possesses advantages such as good wettability, low film resistance, and excellent alkali resistance; Zircon PERL UTP 500 has reportedly exhibited low area resistivity (<0.3 Ωcm²; 30°C; 30 wt% KOH) and long lifespan under strongly alkaline conditions (>500 hours; 30 wt% KOH). Compared to asbestos and PPS cloth, Zirfon has demonstrated superior performance in AWE and is a proven separator that has been used in commercial systems for over 20 years. However, when applied to AWE systems powered by renewable energy, zircon struggles to serve as a safe separator due to the relatively high gas permeability resulting from its mostly porous structure. Furthermore, when AWE operates using renewable energy as a power source, the operating current density varies significantly depending on weather conditions. Furthermore, if an AWE operates at low current densities (under low loads from renewable energy sources), the oxygen production rate decreases, resulting in a higher hydrogen content in the oxygen stream. However, a hydrogen concentration exceeding 4% in the oxygen stream during AWE operation can lead to fatal safety issues such as fires and explosions. Therefore, excellent gas barrier performance is required in AWEs connected to renewable energy sources to ensure safe operation over a wide current density range. Thus, constructing a multi-layered gas barrier layer by controlling the physical structure of the diaphragm can effectively reduce hydrogen-oxygen cross-diffusion and improve the safety of the AWE system.

[0004] When applying for this invention, the applicant, through a search, discovered a Chinese patent disclosed "A Composite Membrane for Hydrogen Production by Electrolysis of Water and its Preparation Method," application number "202211447743.4." This patent mainly involves adding a composite membrane layer containing inorganic ceramic fibers and the main material of the membrane-forming solution to the surface of a mesh-woven substrate. This composite membrane layer is an inorganic-organic composite layer, which significantly improves the stability and hydrophilicity of the composite membrane, increases the membrane current, and reduces the membrane resistance. Although this method can improve the stability and hydrophilicity of the membrane, the inorganic-organic composite layer used in the composite membrane layer may not provide sufficient gas isolation capacity, resulting in an ineffective reduction of gas permeability. Furthermore, although the composite membrane layer can cover the mesh-woven fabric, if the membrane layer cannot be completely sealed or has pores, gas may permeate through these pathways, thereby reducing the gas isolation performance of the membrane. Therefore, technical improvements are urgently needed. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] This solves the problem that traditional composite membranes cannot effectively reduce gas permeability because the slurry cannot be pre-evaporated to form a dense nanoscale gas barrier layer through multiple coatings with varying intervals.

[0007] (II) Technical Solution

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A high-efficiency composite membrane for hydrogen production by water electrolysis with multiple gas barrier layers includes the following materials required in the preparation process: a slit formed by a first scraper, a slit formed by a second scraper, a slit formed by a third scraper, a first component skin layer slurry, a second component skin layer slurry, a third component skin layer slurry, a first skin layer, a second skin layer, a third skin layer, and a substrate.

[0010] The production process includes the following steps:

[0011] S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly.

[0012] S2. Continuously mix the resulting slurry until a uniform viscosity is achieved;

[0013] S3. Pour the suspension into the slit formed by the first scraper containing the first component skin slurry to form the first gas barrier layer;

[0014] S4. Let it stand for a period of time to allow the first gas barrier layer to solidify;

[0015] S5. Pass through the slit formed by the second scraper with the second component skin slurry, and let stand for a period of time to form the second air barrier layer;

[0016] S6. Let it stand for a period of time to allow the second gas barrier layer to solidify;

[0017] S7. Pass through the slit formed by the third scraper with the third component skin slurry, and let it stand for a period of time to form the third air barrier layer;

[0018] S8. Let it stand for a period of time to allow the third gas barrier layer to solidify;

[0019] S9 Repeat the above steps until the required thickness and number of air barrier layers are formed;

[0020] S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water;

[0021] S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

[0022] The above technical solution enables high-efficiency scanning of ceramics by using multiple camera devices working simultaneously. The scanning angles and perspectives are diverse, and the details and textures of the ceramics are clearly captured, ensuring accurate capture of the ceramic's design elements.

[0023] Furthermore, in step S3, the PPS mesh material serves as a supporting material.

[0024] Furthermore, the distance between the scrapers in the slit formed by the first scraper is 100 μm, the distance between the scrapers in the slit formed by the second scraper is 200 μm, and the distance between the scrapers in the slit formed by the third scraper is 300 μm.

[0025] Furthermore, in steps S4, S6, and S8, selective operations are performed during the settling period, such as continuing settling, using forced air convection, or providing a humid environment. These operations are selected as needed to control and adjust the membrane performance.

[0026] Furthermore, the first skin layer is a first membrane formed by a first component skin layer slurry, the second skin layer is a second membrane formed by a second component skin layer slurry, and the third skin layer is a third membrane formed by a third component skin layer slurry.

[0027] Furthermore, the substrate is the basic material for membrane synthesis.

[0028] (III) Beneficial Effects

[0029] This invention provides a high-efficiency composite membrane for hydrogen production via water electrolysis with multiple barrier layers. It possesses the following beneficial effects:

[0030] 1. This invention provides a high-efficiency composite membrane for electrolytic hydrogen production using multiple gas barrier layers. The porous membrane forms a dense nanoscale gas barrier layer by pre-evaporating the slurry through multiple coatings, which can effectively reduce gas permeability. Since the dense gas barrier layer is extremely thin, it does not increase ion resistance. Therefore, it can effectively avoid hydrogen-oxygen cross-linking without increasing electrolysis energy consumption, thus improving the safety of the electrolytic hydrogen production system. Attached Figure Description

[0031] Figure 1 This is a flowchart of a method for preparing a high-efficiency composite membrane for hydrogen production by water electrolysis with multiple gas barrier layers according to the present invention;

[0032] Figure 2 This is a schematic diagram of the synthesis of a multi-layer composite membrane for high-efficiency electrolysis of water to produce hydrogen, which has multiple gas barrier layers according to the present invention.

[0033] Among them, 1. a slit formed by the first scraper; 2. a slit formed by the second scraper; 3. a slit formed by the third scraper; 4. a first component skin layer slurry; 5. a second component skin layer slurry; 6. a third component skin layer slurry; 7. a first skin layer; 8. a second skin layer; 9. a third skin layer; and 10. a substrate. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1:

[0036] like Figure 1-2 As shown, this embodiment of the invention provides a high-efficiency composite membrane for hydrogen production by water electrolysis with multiple gas barrier layers, including the materials required in the preparation process: slit 1 formed by a first scraper, slit 2 formed by a second scraper, slit 3 formed by a third scraper, a first component skin slurry 4, a second component skin slurry 5, a third component skin slurry 6, a first skin layer 7, a second skin layer 8, a third skin layer 9, and a substrate 10.

[0037] The production process includes the following steps:

[0038] S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly.

[0039] S2. Continuously mix the resulting slurry until a uniform viscosity is achieved;

[0040] S3. Pour the suspension into the slit 1 formed by the first scraper containing the first component skin slurry 4 to form the first gas barrier layer. The PPS mesh material acts as a supporting material. The distance between the scrapers in the slit 1 formed by the first scraper is 100um.

[0041] S4. Let it stand for a period of time to allow the first gas barrier layer to solidify;

[0042] S5. The second layer of air barrier is formed by the second scraper 2 with the second component skin slurry 5 and left to stand for a period of time. The distance between the scrapers in the second scraper 2 is 200um.

[0043] S6. Let it stand for a period of time to allow the second gas barrier layer to solidify;

[0044] S7. The third layer of air barrier is formed by the third scraper in the slit 3 with the third component skin slurry 6 and left to stand for a period of time. The distance between the scrapers in the slit 2 formed by the third scraper is 300um.

[0045] S8. Let it stand for a period of time to allow the third gas barrier layer to solidify;

[0046] In steps S4, S6 and S8, selective operations are performed during the settling period, such as continuing settling, using forced air convection or providing a humid environment. These operations are selected as needed to control and adjust the membrane performance.

[0047] S9 Repeat the above steps until the required thickness and number of air barrier layers are formed;

[0048] S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water;

[0049] S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

[0050] The first skin layer 7 is a first membrane formed by the first component skin layer slurry 4, the second skin layer 8 is a second membrane formed by the second component skin layer slurry 5, the third skin layer 9 is a third membrane formed by the third component skin layer slurry 6, and the substrate 10 is the basic material for membrane synthesis.

[0051] Example 2:

[0052] The materials required for the preparation process include: slit 1 formed by the first scraper, slit 2 formed by the second scraper, slit 3 formed by the third scraper, first component skin layer slurry 4, second component skin layer slurry 5, third component skin layer slurry 6, first skin layer 7, second skin layer 8, third skin layer 9 and substrate 10;

[0053] The production process includes the following steps:

[0054] S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly.

[0055] S2. Continuously mix the resulting slurry until a uniform viscosity is achieved;

[0056] S3. Pour the suspension into the slit 1 formed by the first scraper containing the first component skin slurry 4 to form the first gas barrier layer;

[0057] S4. Let it stand for a period of time to allow the first gas barrier layer to solidify;

[0058] S5. Pass through the second slit 2 formed by the second scraper with the second component skin slurry 5, and let it stand for a period of time to form the second air barrier layer;

[0059] S6. Let it stand for a period of time to allow the second gas barrier layer to solidify;

[0060] S7. The third layer of air barrier is formed by the third scraper with the third component skin slurry 6 and left to stand for a period of time.

[0061] S8. Let it stand for a period of time to allow the third gas barrier layer to solidify;

[0062] S9 Repeat the above steps until the required thickness and number of air barrier layers are formed;

[0063] S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water;

[0064] S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

[0065] PPS mesh support: Pass the sample through a 200µm wide scraper slit in group 1 and let it stand for 5-30 seconds; pass it through a 400µm wide scraper slit in group 2 and let it stand for 5-30 seconds; pass it through a 600µm wide scraper slit in group 3 and let it stand for 5-30 seconds; place the sample in pure water for phase inversion, then wash it several times with distilled water and store it in deionized water to form a composite membrane with multiple gas barrier layers. The preferred standing time is 15 seconds.

[0066] Example 3:

[0067] The materials required for the preparation process include: slit 1 formed by the first scraper, slit 2 formed by the second scraper, slit 3 formed by the third scraper, first component skin layer slurry 4, second component skin layer slurry 5, third component skin layer slurry 6, first skin layer 7, second skin layer 8, third skin layer 9 and substrate 10;

[0068] The production process includes the following steps:

[0069] S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly.

[0070] S2. Continuously mix the resulting slurry until a uniform viscosity is achieved;

[0071] S3. Pour the suspension into the slit 1 formed by the first scraper containing the first component skin slurry 4 to form the first gas barrier layer;

[0072] S4. Let it stand for a period of time to allow the first gas barrier layer to solidify;

[0073] S5. Pass through the second slit 2 formed by the second scraper with the second component skin slurry 5, and let it stand for a period of time to form the second air barrier layer;

[0074] S6. Let it stand for a period of time to allow the second gas barrier layer to solidify;

[0075] S7. The third layer of air barrier is formed by the third scraper with the third component skin slurry 6 and left to stand for a period of time.

[0076] S8. Let it stand for a period of time to allow the third gas barrier layer to solidify;

[0077] S9 Repeat the above steps until the required thickness and number of air barrier layers are formed;

[0078] S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water;

[0079] S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

[0080] PPS mesh support: Forced air convection is applied for 1-20 seconds through the first group of 200µm wide scraper slits; forced air convection is applied for 1-20 seconds through the second group of 400µm wide scraper slits; forced air convection is applied for 1-20 seconds through the third group of 600µm wide scraper slits; the sample is placed in pure water for phase inversion, then washed several times with distilled water and stored in deionized water to form a composite membrane with multiple gas barrier layers. The preferred forced air convection time is 10 seconds.

[0081] Example 4:

[0082] The materials required for the preparation process include: slit 1 formed by the first scraper, slit 2 formed by the second scraper, slit 3 formed by the third scraper, first component skin layer slurry 4, second component skin layer slurry 5, third component skin layer slurry 6, first skin layer 7, second skin layer 8, third skin layer 9 and substrate 10;

[0083] The production process includes the following steps:

[0084] S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly.

[0085] S2. Continuously mix the resulting slurry until a uniform viscosity is achieved;

[0086] S3. Pour the suspension into the slit 1 formed by the first scraper containing the first component skin slurry 4 to form the first gas barrier layer;

[0087] S4. Let it stand for a period of time to allow the first gas barrier layer to solidify;

[0088] S5. Pass through the second slit 2 formed by the second scraper with the second component skin slurry 5, and let it stand for a period of time to form the second air barrier layer;

[0089] S6. Let it stand for a period of time to allow the second gas barrier layer to solidify;

[0090] S7. The third layer of air barrier is formed by the third scraper with the third component skin slurry 6 and left to stand for a period of time.

[0091] S8. Let it stand for a period of time to allow the third gas barrier layer to solidify;

[0092] S9 Repeat the above steps until the required thickness and number of air barrier layers are formed;

[0093] S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water;

[0094] S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

[0095] PPS mesh support: The sample is passed through a 200µm wide scraper slit in the first group, under humidified airflow for 1-15 seconds; through a 400µm wide scraper slit in the second group, under humidified airflow for 1-15 seconds; and through a 600µm wide scraper slit in the third group, under humidified airflow for 1-15 seconds. The sample is then placed in pure water for phase inversion, washed several times with distilled water, and stored in deionized water to form a composite membrane with multiple gas barrier layers. The preferred humidified airflow time is 5 seconds.

[0096] Performance tests are as follows:

[0097] sample Example 1 Example 2 Example 3 Agfa sample Porosity (%) 61.3 60.1 59.2 55.3 <![CDATA[Sheet Resistance (Ωcm 2 ) * > 0.25 0.21 0.20 0.23 Bubble point (bar) 3.1 4.0 6.2 2.0 Hydrogen concentration in oxygen (%) 0.5 0.4 0.3 1.0

[0098] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency composite membrane for hydrogen production via water electrolysis with multiple barrier layers, characterized in that, The materials required for the preparation process include: slits formed by the first scraper (1), slits formed by the second scraper (2), slits formed by the third scraper (3), first component skin layer slurry (4), second component skin layer slurry (5), third component skin layer slurry (6), first skin layer (7), second skin layer (8), third skin layer (9) and substrate (10); The production process includes the following steps: S1. PVP, PSU and NMP were mixed in a stirring device as solvents, and ZrO2 nanoparticles were added and stirred evenly. S2. Continuously mix the resulting slurry until a uniform viscosity is achieved; S3. Pour the suspension into the slit (1) formed by the first scraper containing the first component skin slurry (4) to form the first gas barrier layer; S4. Let it stand for a period of time to allow the first gas barrier layer to solidify; S5. The second layer of air barrier is formed by a second scraper with a second component skin slurry (5) and left to stand for a period of time. S6. Let it stand for a period of time to allow the second gas barrier layer to solidify; S7. The third layer of air barrier is formed by the third scraper with the third component skin slurry (6) and left to stand for a period of time. S8. Let it stand for a period of time to allow the third gas barrier layer to solidify; S9 Repeat the above steps until the required thickness and number of air barrier layers are formed; S10. Place the sample in the effluent for phase inversion, and then wash it multiple times with distilled water; S11. Finally, the sample is stored in deionized water to form a composite membrane with multiple gas barrier layers.

2. The high-efficiency composite membrane for electrolytic hydrogen production via water splitting with multiple gas barrier layers according to claim 1, characterized in that, In step S3, the PPS mesh material serves as a supporting material.

3. The high-efficiency composite membrane for electrolytic hydrogen production via water electrolysis with multiple barrier layers according to claim 1, characterized in that, The distance between the scrapers in the slit (1) formed by the first scraper is 100 μm, the distance between the scrapers in the slit (2) formed by the second scraper is 200 μm, and the distance between the scrapers in the slit (2) formed by the third scraper is 300 μm.

4. The high-efficiency composite membrane for electrolytic hydrogen production via water electrolysis with multiple barrier layers according to claim 1, characterized in that, In steps S4, S6, and S8, selective operations are performed during the settling period, such as continuing settling, using forced air convection, or providing a humid environment. These operations are selected as needed to control and adjust the membrane performance.

5. The high-efficiency composite membrane for electrolytic hydrogen production via water electrolysis with multiple barrier layers according to claim 1, characterized in that, The first skin layer (7) is a first membrane formed by the first component skin layer slurry (4), the second skin layer (8) is a second membrane formed by the second component skin layer slurry (5), and the third skin layer (9) is a third membrane formed by the third component skin layer slurry (6).

6. The high-efficiency composite membrane for hydrogen production via water electrolysis with multiple barrier layers according to claim 1, characterized in that, The substrate (10) is the basic material for membrane synthesis.

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