Electrolytic cell and anion exchange conductive hollow fiber tube matrix thereof
By combining a conductive hollow fiber tube matrix with a catalyst, the problems of high mass transfer resistance and high energy consumption in AEM electrolytic cells are solved, achieving low-energy and high-efficiency hydrogen production. Oxygen is directly discharged without mixing into the water, reducing alkalinity and water content.
Patent Information
- Application Number
- CN202510832420.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-08-08
- Filing Date
- 2025-06-20
- Publication Date
- 2025-09-16
AI Technical Summary
Existing AEM electrolytic cells have problems in hydrogen production, such as high mass transfer resistance, high energy consumption, oxygen bubbles hindering the contact between the anode and the electrolyte, and high alkalinity and high water content caused by the mixing of oxygen and water.
A conductive hollow fiber tube matrix is used as the ion exchange interface. Water or electrolyte is directly introduced into the conductive hollow fiber tube. By utilizing anisotropic diffusion and a large mass transfer area, combined with a catalytic and non-electric photocatalytic or chemical energy hydrogen production mechanism, the mass transfer resistance is reduced and the hydrogen production efficiency is improved.
It achieves hydrogen production with low energy consumption, reduces mass transfer resistance, maintains effective electrode area, allows oxygen to be directly discharged without mixing into water, reduces alkalinity and water content, and achieves efficient and stable hydrogen production.
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Figure CN120649043A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to an electrolytic cell and its anion exchange conductive hollow fiber tube matrix. Specifically, the present invention relates to a matrix membrane composed of conductive hollow fiber tubes that serves as the ion exchange interface between the anode and cathode of the electrolytic cell. Water or electrolyte is directly introduced into the conductive hollow fiber tubes. Compared to existing AEM electrolytic cells, this method has lower mass transfer resistance and can produce hydrogen with lower energy consumption. Background Art
[0002] The product of hydrogen combustion is water, and it does not emit greenhouse gases such as carbon dioxide. It is an important green energy. The electrolysis of water to produce hydrogen is an effective source of hydrogen. In the future, combined with solar energy and wind power, it will be an important hydrogen production solution for obtaining clean green hydrogen.
[0003] The principle of hydrogen production by electrolysis of water is to form a circuit of anode, cathode, and water or electrolyte in the electrolytic cell to form an electrolytic cell. After the current is passed through, the water undergoes an oxidation-reduction reaction to produce hydrogen at the cathode and oxygen at the anode.
[0004] See Figure 10 As shown, anion exchange membrane electrolysis (AEM electrolysis) can use water or a low-concentration electrolyte to electrolyze water to produce hydrogen. The AEM electrolysis cell includes an anion exchange membrane A placed between an anode B and a cathode C, with an electrolytic cell D connected to anode B. After turning on the power, water in electrolytic cell D is passed into anode B. Water molecules diffuse through anion exchange membrane A and enter cathode C, where they decompose to produce hydrogen and hydroxide ions. The hydroxide ions diffuse through anion exchange membrane A and return to anode B to produce oxygen. The oxygen flows back to electrolytic cell D and is discharged through an exhaust valve. The diffusion of water molecules and hydroxide ions in anion exchange membrane A is isotropic, and the only surface area of anion exchange membrane A is the membrane surface.
[0005] According to test results, the AEM electrolysis cell consumes approximately 50 to 55 kWh of energy to produce 1 kilogram of hydrogen. This high energy consumption is primarily due to the small mass transfer area and the high mass transfer resistance caused by oxygen bubbles during oxygen generation, which hinder the contact between the anode and the electrolyte or water.
[0006] Furthermore, since the oxygen in the AEM electrolysis cell is generated at the anode / electrolyte interface (bubbling), it will return to the electrolysis cell and then be discharged. Therefore, it will mix with some water or electrolyte, resulting in higher alkalinity and water content of the discharged oxygen. Summary of the Invention
[0007] In view of the above problems, an object of the present invention is to provide an electrolytic cell and an anion exchange conductive hollow fiber tube matrix thereof.
[0008] The present invention provides an anion exchange conductive hollow fiber tube matrix comprising:
[0009] A plurality of conductive hollow fiber tubes are adjacently arranged in a matrix. The conductive hollow fiber tubes have a diffusion surface and are respectively provided with an inlet and an outlet at two opposite ends.
[0010] The electrolytic cell comprises:
[0011] The anion exchange conductive hollow fiber tube matrix includes an anode and a cathode disposed adjacent to the diffusion surface. An electrolytic cell communicates with the inlet and the outlet. A power source is connected to the anode and the cathode.
[0012] During operation, the power supply is turned on, and water in the electrolytic cell enters the conductive hollow fiber tube from the inlet. Water molecules enter the cathode from the diffusion surface and decompose to produce hydrogen and hydroxide ions. Hydrogen is discharged from the cathode, and hydroxide ions return to the conductive hollow fiber tube from the diffusion surface and then enter the anode from the diffusion surface to produce oxygen. Oxygen is discharged from the anode surface, and water returns to the electrolytic cell from the outlet.
[0013] Furthermore, the conductive hollow fiber tube is subjected to ammonium treatment.
[0014] Furthermore, a catalyst is disposed between the anion exchange conductive hollow fiber tube matrix and the anode, and between the anion exchange conductive hollow fiber tube matrix and the cathode. Specifically, the catalyst may be a nickel / iron alloy oxide. Furthermore, the catalyst may be coated on the diffusion surface of the conductive hollow fiber tube.
[0015] Furthermore, a conductive carbon fiber diffusion layer is arranged between the anion exchange conductive hollow fiber tube matrix and the anode, and between the anion exchange conductive hollow fiber tube matrix and the cathode.
[0016] Furthermore, there is a non-electric photocatalytic hydrogen production mechanism, which includes a water supply tank, a first photocatalyst arranged in the water supply tank and connected to the anode, and a second photocatalyst arranged in the water supply tank and connected to the cathode. The first photocatalyst and the second photocatalyst produce hydrogen at the adjacent cathode through a photoreaction, and produce oxygen at the adjacent anode.
[0017] Furthermore, there is a non-electric chemical energy hydrogen production mechanism, which includes a reaction tank. By inputting chemical agents into the reaction tank for reaction, hydrogen is generated at the adjacent cathode and oxygen is generated at the adjacent anode.
[0018] Furthermore, the conductive hollow fiber tube is manufactured by forming regular or irregular pores in a conductive film.
[0019] The above technical features can achieve the following effects:
[0020] 1. In the electrolytic cell of the present invention, water or electrolyte is directly introduced into the anion exchange conductive hollow fiber tube matrix, and oxygen is generated and discharged directly on the wet anode surface. No oxygen bubbles hinder the contact between the anode and the electrolyte or water. Therefore, the mass transfer resistance can be reduced and the effective area of the electrode can be maintained. According to experiments, only approximately 40KWh to 45KWh of energy is required to produce 1 kg of hydrogen. Compared with the AEM electrolytic cell that requires approximately 50KWh to 55KWh of energy per kg of hydrogen produced, the electrolytic cell of the present invention can produce hydrogen with lower energy consumption.
[0021] 2. In the electrolytic cell of the present invention, the diffusion of water molecules and hydroxide ions in the anion exchange conductive hollow fiber tube matrix is anisotropic. The anion exchange conductive hollow fiber tube matrix has a large mass transfer area (the wall of each conductive hollow fiber tube serves as a mass transfer surface). A large mass transfer area can lead to better performance and lower power consumption.
[0022] 3. When the electrolytic cell of the present invention electrolyzes water to produce hydrogen, the oxygen generated on the anode surface will not be mixed into the water or electrolyte but will be discharged directly from the anode surface, thereby achieving oxygen collection with lower alkalinity, low water content and high pressure.
[0023] 4. The electrolytic cell of the present invention can be equipped with a non-electric photocatalytic hydrogen production mechanism or a non-electric chemical hydrogen production mechanism, so that hydrogen can be continuously and stably produced by the non-electric photocatalytic hydrogen production mechanism or the non-electric chemical hydrogen production mechanism even when no electricity is provided. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is a three-dimensional appearance diagram of the anion exchange conductive hollow fiber tube matrix of the electrolytic cell of the present invention.
[0025] Figure 2 Schematic diagram of the electrolytic cell of the present invention.
[0026] Figure 3 This is a schematic diagram of the electrolytic cell of the present invention, which shows that water or electrolyte is passed into the anion exchange conductive hollow fiber tube matrix and diffuses when the electrolytic cell electrolyzes water to produce hydrogen.
[0027] Figure 4 The figure is a graph showing the electrolysis voltage of the electrolysis cell of the present invention and the conventional AEM electrolysis cell at the same current density when electrolyzing water.
[0028] Figure 5The graph shows the electrolysis voltage of the electrolysis cell of the present invention and the conventional AEM electrolysis cell when electrolyzing water under the same hydrogen production rate, number of cell stacks, and current conditions.
[0029] Figure 6 Schematic diagram of an electrolytic cell of the present invention in which a catalyst and a conductive carbon fiber diffusion layer are arranged between the anion exchange conductive hollow fiber tube matrix and the anode / cathode.
[0030] Figure 7A This is a schematic diagram of the catalyst coating on the conductive hollow fiber tube of the anion exchange conductive hollow fiber tube matrix of the present invention.
[0031] Figure 7B This is the second schematic diagram of the catalyst coating on the conductive hollow fiber tube of the anion exchange conductive hollow fiber tube matrix of the present invention.
[0032] Figure 7C This is the third schematic diagram of the catalyst coating on the conductive hollow fiber tube of the anion exchange conductive hollow fiber tube matrix of the present invention.
[0033] Figure 8 This is a schematic diagram of an electrolytic cell of the present invention with a non-electric photocatalytic hydrogen production mechanism added.
[0034] Figure 9 Schematic diagram of an electrolytic cell of the present invention with an additional non-electric chemical energy hydrogen production mechanism.
[0035] Figure 10 Schematic diagram of an existing AEM electrolysis cell.
[0036] Figure 11 This is a schematic diagram of manufacturing a plurality of straight strip-shaped, regularly arranged continuous holes on a conductive film to form a conductive hollow fiber tube in an embodiment of the present invention.
[0037] Figure 12 Schematic diagram of a conductive hollow fiber tube formed by forming a plurality of spirally regularly arranged continuous holes on a conductive film in an embodiment of the present invention.
[0038] Figure 13 This is a schematic diagram of a conductive hollow fiber tube formed by making a plurality of straight, staggered, and irregularly arranged continuous holes on a conductive film in an embodiment of the present invention.
[0039] Figure 14 This is a schematic diagram of making a plurality of irregularly arranged holes of different sizes on a conductive film to form a conductive hollow fiber tube in an embodiment of the present invention.
[0040] Explanation of the accompanying symbols: 10-anion exchange conductive hollow fiber tube matrix; 1-conductive hollow fiber tube; 11-diffusion surface; 12-inlet; 13-outlet; 14-pore; 20-anode; 30-cathode; 40-electrolyzer; 50-catalyst; 60-conductive carbon fiber diffusion layer; 70-non-electric photocatalyst hydrogen production mechanism; 701-water supply tank; 702-first photocatalyst; 703-second photocatalyst; 704-voltmeter; 80-non-electric chemical energy hydrogen production mechanism; 801-reaction tank; A-anion exchange membrane; B-anode; C-cathode; D-electrolyzer. DETAILED DESCRIPTION
[0041] The following embodiments are merely provided to assist in explaining the possible implementations of the electrolytic cell and the anion exchange conductive hollow fiber tube matrix of the present invention, and are not intended to limit the present invention.
[0042] See Figure 1 As shown, the anion exchange conductive hollow fiber tube matrix 10 of this embodiment comprises: a plurality of conductive hollow fiber tubes 1 arranged adjacently in a matrix. Each conductive hollow fiber tube 1 has a diffusion surface 11, an inlet 12, and an outlet 13 at opposite ends. The conductive hollow fiber tubes 1 can be made of conductive carbon fibers. The anion exchange conductive hollow fiber tube matrix 10 of this embodiment comprises a plurality of conductive hollow fiber tubes 1 arranged into a 10 cm x 10 cm film with a thickness of approximately 20 μm. The flow channel diameter of each conductive hollow fiber tube 1 is approximately 5 μm to 15 μm. The conductive hollow fiber tubes 1 are ammonium treated to form (NH4+) ammonium ion functional groups on the polymer conductive hollow fiber tubes 1. The ammonium ion functional groups allow the passage of (OH-) hydroxide ions, a key medium for water electrolysis, thereby imparting anion conductivity.
[0043] Figures 11 to 14 As shown, in addition to arranging a plurality of individual conductive hollow fiber tubes 1 to form the anion exchange conductive hollow fiber tube matrix 10, the conductive hollow fiber tubes 1 can also be manufactured by regularly or irregularly forming pores in a conductive film and then arranged to form the anion exchange conductive hollow fiber tube matrix 10. For example Figure 11 A plurality of straight and regularly arranged continuous holes 14 are made on a conductive film to form the conductive hollow fiber tube 1; Figure 12 A plurality of spirally regularly arranged continuous holes 14 are formed on a conductive film to form the conductive hollow fiber tube 1; Figure 13 A plurality of straight, staggered, and irregularly arranged continuous holes 14 are formed on a conductive film to form the conductive hollow fiber tube; Figure 14 A plurality of irregularly arranged holes 14 of different sizes are made on a conductive film to form the conductive hollow fiber tube 1 .
[0044] See Figure 2 As shown, the electrolytic cell of this embodiment includes: the anion exchange conductive hollow fiber tube matrix 10; an anode 20 and a cathode 30 disposed adjacent to the diffusion surface 11. Preferably, the anode 20 and cathode 30 are disposed on opposite sides of the anion exchange conductive hollow fiber tube matrix 10. In this embodiment, the anode 20 and cathode 30 utilize nickel foam electrodes; an electrolytic cell 40 communicating with the inlet 12 and the outlet 13; and a power supply connected to the anode 20 and cathode 30 (connecting the power supply to the anode 20 and cathode 30 is conventional and therefore not shown in the figure).
[0045] See Figure 2 and Figure 3 As shown, during operation, the power is turned on, and water in the electrolytic cell 40 enters the conductive hollow fiber tube 1 from the inlet 12. The water molecules enter the cathode 30 from the diffusion surface 11 and decompose to produce hydrogen and hydroxide ions. The hydrogen is discharged from the cathode 30, and the hydroxide ions return to the conductive hollow fiber tube 1 from the diffusion surface 11 and then enter the anode 20 from the diffusion surface 11 to produce oxygen. The oxygen is directly discharged from the surface of the anode 20, and the water returns to the electrolytic cell 40 from the outlet 13. The diffusion of water molecules and hydroxide ions in the anion exchange conductive hollow fiber tube matrix 10 is anisotropic. The anion exchange conductive hollow fiber tube matrix 10 has a large mass transfer area (the wall of each conductive hollow fiber tube 1 serves as a mass transfer surface). A large mass transfer area can lead to better performance and lower power consumption. In the electrolytic cell of the present invention, water or electrolyte is directly introduced into the anion exchange conductive hollow fiber tube matrix 10, and oxygen is generated and discharged directly on the wet surface of the anode 20. There are no oxygen bubbles that hinder the contact between the anode 20 and the electrolyte or water. Therefore, the mass transfer resistance is reduced, the effective area of the electrode is maintained, and the hydrogen production efficiency is improved.
[0046] See Figure 4 As shown, due to the larger mass transfer area, reduced mass transfer resistance and ability to maintain the effective electrode area, the electrolysis cell of the present invention has a lower electrolysis voltage than the conventional AEM electrolysis cell when the same current density is applied.
[0047] See Figure 5 As shown, the electrolysis cell of the present invention and the existing AEM electrolysis cell are operated continuously for 400 minutes under the same hydrogen production rate, the same number of cell stacks and the same current conditions. The electrolysis cell of the present invention has a lower electrolysis voltage than the existing AEM electrolysis cell.
[0048] According to the above description and tests, the electrolysis cell of the present invention only requires about 40KWh to 45KWh of energy consumption to produce 1 kg of hydrogen. Compared with the AEM electrolysis cell, which requires about 50KWh to 55KWh of energy consumption to produce 1 kg of hydrogen, the electrolysis cell of the present invention can produce hydrogen at a lower energy consumption.
[0049] In addition, when the electrolytic cell of the present invention electrolyzes water to produce hydrogen, the oxygen generated on the surface of the anode 20 will not be mixed into the water or electrolyte but will be directly discharged from the surface of the anode 20, thereby achieving oxygen collection with lower alkalinity, low water content and high pressure.
[0050] See Figure 6 As shown, to improve ion diffusion efficiency, the electrolysis cell may further include a catalyst 50 and a conductive carbon fiber diffusion layer 60 disposed between the anion exchange conductive hollow fiber tube matrix 10 and the anode 20, and between the anion exchange conductive hollow fiber tube matrix 10 and the cathode 30. Specifically, the catalyst 50 may be a nickel / iron alloy oxide. The catalyst 50 may be prepared as a slurry and coated on the conductive carbon fiber diffusion layer 60, which is a porous carbon fiber. The catalyst 50 may be adsorbed on the surface of the conductive carbon fiber diffusion layer 60 and then dried to form a thin film. The catalyst 50 can reduce the activation energy of water electrolysis in an alkaline environment, making it easier for water to decompose (dissociate) into hydrogen ions and hydroxide ions. The hydroxide ions are easily oxidized to oxygen. Therefore, the presence of the catalyst 50 can reduce energy consumption during water electrolysis and improve hydrogen production efficiency.
[0051] See 7A to 7C As shown, the catalyst 50 can also be coated on the diffusion surface 11 of the conductive hollow fiber tube 1, for example Figure 7A The catalyst 50 is coated on the inner and outer surfaces of the diffusion surface 11 of the conductive hollow fiber tube 1, for example Figure 7B The catalyst 50 is coated on the outside of the diffusion surface 11 of the conductive hollow fiber tube 1, for example Figure 7C The catalyst 50 is coated on the inner surface of the diffusion surface 11 of the conductive hollow fiber tube 1. This can increase the specific surface area of the catalyst 50 for reaction and improve the reaction efficiency.
[0052] See Figure 8As shown, a non-electric photocatalytic hydrogen production mechanism 70 can be added to the electrolytic cell. The non-electric photocatalytic hydrogen production mechanism 70 includes a water supply tank 701, a first photocatalyst 702 disposed in the water supply tank 701 and connected to the anode 20, and a second photocatalyst 703 disposed in the water supply tank 701 and connected to the cathode 30. A voltmeter 704 is connected between the anode 20 and the cathode 30. The first photocatalyst 702 and the second photocatalyst 703 produce hydrogen adjacent to the cathode 30 and oxygen adjacent to the anode 20 through a photoreaction, and the voltage value can be read by the voltmeter 704. In this way, the non-electric photocatalytic hydrogen production mechanism 70 can still stably and continuously produce hydrogen even without power supply.
[0053] See Figure 9 As shown, a non-electric chemical hydrogen production mechanism 80 can be added to the electrolysis cell. The non-electric chemical hydrogen production mechanism 80 includes a reaction tank 801. Chemical agents are introduced into the reaction tank 801 to react with alkali metals or alkaline earth metals, for example, using an acidic solution or an alkaline solution to react with the alkali metal or alkaline earth metal to produce hydrogen adjacent to the cathode 30 and oxygen adjacent to the anode 20. In this way, the electrochemical hydrogen production mechanism 80 can still produce hydrogen stably and continuously even without power supply.
[0054] From the description of the above embodiments, one can fully understand the operation, use, and effects of the present invention. However, the above embodiments are merely preferred embodiments of the present invention and should not limit the scope of the present invention. In other words, simple equivalent changes and modifications made in accordance with the claims and the description of the present invention are all within the scope of the present invention.
Claims
1. An anion exchange conductive hollow fiber tube matrix for an electrolytic cell, characterized in that: include: A plurality of conductive hollow fiber tubes are arranged adjacent to each other in a matrix, each of the conductive hollow fiber tubes having a diffusion surface and an inlet and an outlet at opposite ends thereof; An anode and a cathode of an electrolytic cell are disposed adjacent to the diffusion surface, an electrolytic cell of the electrolytic cell is connected to the inlet and the outlet, and a power source is connected to the anode and the cathode. The power source is turned on, and water in the electrolytic cell enters the conductive hollow fiber tube from the inlet. Water molecules enter the cathode from the diffusion surface and decompose to produce hydrogen and hydroxide ions. The hydrogen is discharged from the cathode, and the hydroxide ions return to the conductive hollow fiber tube from the diffusion surface and then enter the anode from the diffusion surface to produce oxygen. The oxygen is discharged from the anode surface, and the water returns to the electrolytic cell from the outlet.
2. The anion exchange conductive hollow fiber tube matrix of the electrolytic cell according to claim 1, characterized in that The conductive hollow fiber tube is subjected to ammonium treatment.
3. The anion exchange conductive hollow fiber tube matrix of the electrolytic cell according to claim 1, characterized in that A catalyst is coated on the diffusion surface of the conductive hollow fiber tube.
4. The anion exchange conductive hollow fiber tube matrix of the electrolytic cell according to claim 3, characterized in that The catalyst is nickel / iron alloy oxide.
5. The anion exchange conductive hollow fiber tube matrix of the electrolytic cell according to claim 1, characterized in that The conductive hollow fiber tube is manufactured by forming regular or irregular pores on a conductive film.
6. An electrolytic cell, characterized in that include: An anion exchange conductive hollow fiber tube matrix, comprising a plurality of conductive hollow fiber tubes arranged adjacent to each other in a matrix, each conductive hollow fiber tube having a diffusion surface and an inlet and an outlet at opposite ends thereof; an anode and a cathode disposed adjacent to the diffusion surface; an electrolytic cell, communicating with the inlet and the outlet; a power source connected to the anode and the cathode; The power supply is turned on, and water in the electrolytic cell enters the conductive hollow fiber tube from the inlet. Water molecules enter the cathode from the diffusion surface and decompose to produce hydrogen and hydroxide ions. Hydrogen is discharged from the cathode, and hydroxide ions return to the conductive hollow fiber tube from the diffusion surface and then enter the anode from the diffusion surface to produce oxygen. Oxygen is discharged from the anode surface, and water returns to the electrolytic cell from the outlet.
7. The electrolytic cell according to claim 6, wherein The conductive hollow fiber tube is subjected to ammonium treatment.
8. The electrolytic cell according to claim 6, wherein A catalyst is arranged between the anion exchange conductive hollow fiber tube matrix and the anode, and between the anion exchange conductive hollow fiber tube matrix and the cathode.
9. The electrolytic cell according to claim 8, wherein The catalyst is coated on the diffusion surface of the conductive hollow fiber tube.
10. The electrolytic cell according to claim 8, wherein The catalyst is nickel / iron alloy oxide.
11. The electrolytic cell according to claim 6, wherein A conductive carbon fiber diffusion layer is arranged between the anion exchange conductive hollow fiber tube matrix and the anode, and between the anion exchange conductive hollow fiber tube matrix and the cathode.
12. The electrolytic cell according to claim 6, wherein A non-electric photocatalytic hydrogen production mechanism is provided, which includes a water supply tank, a first photocatalyst disposed in the water supply tank and connected to the anode, and a second photocatalyst disposed in the water supply tank and connected to the cathode. The first photocatalyst and the second photocatalyst generate hydrogen adjacent to the cathode and generate oxygen adjacent to the anode through a photoreaction.
13. The electrolytic cell according to claim 6, wherein A non-electric chemical energy hydrogen production mechanism includes a reaction tank. By inputting chemical reagents into the reaction tank for reaction, hydrogen is generated at the adjacent cathode and oxygen is generated at the adjacent anode.
14. The electrolytic cell according to claim 6, wherein The conductive hollow fiber tube is manufactured by forming regular or irregular pores on a conductive film.