Electrolysis hydrogen production system

Abstract

This application discloses an electrolytic hydrogen production system, belonging to the field of electrolytic hydrogen production. The electrolytic hydrogen production system includes: an electrolytic cell forming isolated anode and cathode chambers; an anode storage tank connected end-to-end to the anode chambers for storing the anolyte, wherein the electrolyte in the anolyte includes a water-soluble redox pair; and a cathode storage tank connected end-to-end to the cathode chambers for storing the cathode electrolyte. By adding a water-soluble redox pair to the anolyte in the electrolytic cell, an oxidation reaction occurs during hydrogen production. No oxygen is produced at the anode, and hydrogen is produced at the cathode, avoiding the formation of an explosive gas mixture from oxygen and hydrogen. This improves the safety of the electrolytic hydrogen production system, expands the power operating range, and the high-potential products after anode oxidation can be used as raw materials for power generation, improving the utilization rate of the anode products.

Description

Technical Field

[0001] This application belongs to the field of hydrogen electrolysis technology, and particularly relates to an hydrogen electrolysis system. Background Technology

[0002] Existing electrolysis hydrogen production systems have high energy consumption and low safety. Summary of the Invention

[0003] This application aims to address at least one of the technical problems existing in related technologies. To this end, this application proposes an electrolytic hydrogen production system with high safety.

[0004] In a first aspect, this application provides an electrolytic hydrogen production system, comprising:

[0005] The electrolytic cell forms isolated anode and cathode chambers;

[0006] An anode storage container, connected end-to-end to the anode chamber, is used to store the anolyte, wherein the electrolyte in the anolyte includes a water-soluble redox pair;

[0007] A cathode reservoir, connected end-to-end to the cathode chamber, is used to store cathode electrolyte.

[0008] According to the electrolytic hydrogen production system of this application, by adding water-soluble redox pairs to the anolyte of the electrolytic cell, an oxidation reaction is carried out during the electrolytic hydrogen production process. No oxygen is produced at the anode, and hydrogen is produced at the cathode. This avoids the formation of explosive gases from the mixing of oxygen and hydrogen, improves the safety of the electrolytic hydrogen production system, expands the power operating range, and the high-potential products after anode oxidation can be used as raw materials for power generation, thus improving the utilization rate of anode products.

[0009] According to one embodiment of this application, the electrolyte in the anolyte comprises a halogen salt.

[0010] According to the electrolytic hydrogen production system of this application, by adding a halide salt to the electrolyte in the anolyte, the oxidation reaction of water-soluble ions occurs at the anode during electrolysis, and no oxygen is produced at the anode, thereby improving the safety of the electrolytic hydrogen production system.

[0011] According to one embodiment of this application, the electrolyte in the anolyte includes bromide salts, iodide salts, hydroquinone sulfonic acid, or hydroquinone sulfonate.

[0012] According to the electrolytic hydrogen production system of this application, by adding bromide salts, iodide salts, hydroquinone sulfonic acid or hydroquinone sulfonate to the electrolyte in the anolyte, the oxidation reaction of water-soluble ions occurs at the anode during electrolysis, and no oxygen is produced at the anode, thereby improving the safety of the electrolytic hydrogen production system.

[0013] According to one embodiment of this application, the electrolyte contains an acid or a base.

[0014] According to the electrolytic hydrogen production system of this application, hydrogen gas is produced by a hydrogen evolution reaction in an electrolyte containing acid or alkali.

[0015] According to one embodiment of this application, the anode electrode of the electrolytic cell includes at least one of carbon fiber, graphite, titanium, and boron-doped diamond.

[0016] According to the electrolytic hydrogen production system of this application, by selecting at least one of carbon fiber, graphite, titanium, and boron-doped diamond as the anode electrode, the occurrence of oxygen evolution reaction at the anode is reduced.

[0017] According to one embodiment of this application, the cathode electrode of the electrolyzer comprises at least one of a carbon-supported platinum catalyst and a nickel-hydrogen battery negative electrode hydrogen storage alloy.

[0018] According to the electrolytic hydrogen production system of this application, by selecting at least one of carbon-supported platinum catalyst and nickel-hydrogen battery negative electrode hydrogen storage alloy as the cathode electrode, the electrolytic hydrogen production system can have both electrolytic hydrogen production and power generation capabilities.

[0019] According to one embodiment of this application, the cathode electrode of the electrolytic cell includes at least one of Raney nickel catalyst and nickel-molybdenum alloy catalyst.

[0020] According to the electrolytic hydrogen production system of this application, by selecting at least one of Raney nickel catalyst and nickel-molybdenum alloy catalyst as the cathode electrode, the electrolytic hydrogen production system can be equipped with the ability to produce hydrogen by electrolysis.

[0021] According to one embodiment of this application, it also includes:

[0022] A hydrogen storage device is connected to the outlet of the cathode storage device;

[0023] A cathode replenishment pipe is connected to the replenishment port of the cathode reservoir;

[0024] An anode replenishment pipe is connected to the replenishment port of the anode reservoir;

[0025] The anode drain pipe is connected to the drain port of the anode reservoir.

[0026] According to the electrolytic hydrogen production system of this application, hydrogen produced by electrolytic hydrogen production is stored in a hydrogen storage tank, water required for electrolytic hydrogen production is replenished to the cathode storage tank through a cathode replenishment pipe, bromide ions or bromate ions are replenished to the anode storage tank through an anode replenishment pipe, and a mixed solution with a high bromate concentration is discharged from the anode storage tank through an anode drain pipe, thereby maintaining the continuous electrolytic hydrogen production and power generation capabilities of the electrolytic hydrogen production system.

[0027] According to one embodiment of this application, the electrolytic hydrogen production system has a hydrogen production mode;

[0028] In the hydrogen production mode, the outlet of the cathode storage is used to supply hydrogen to the hydrogen storage. When the concentration of oxidation products in the anode storage is greater than a first target value, the anode drain pipe is used to drain the anode electrolyte in the anode storage, and the anode replenishment pipe is used to replenish the anode storage.

[0029] According to the electrolytic hydrogen production system of this application, the hydrogen production mode is set by the electrolytic hydrogen production system. When the concentration of oxidation products in the anode storage is greater than the first target value, the anode drain pipe discharges the anode electrolyte in the anode storage and the anode replenishment pipe replenishes the anode storage, so as to achieve continuous hydrogen production and reduce oxygen evolution.

[0030] According to one embodiment of this application, the outlet of the hydrogen storage device is connected to the inlet of the cathode chamber.

[0031] According to the electrolytic hydrogen production system of this application, by connecting the outlet of the hydrogen storage tank to the inlet of the cathode chamber, the gas in the hydrogen storage tank can enter the cathode chamber through the gas pipe, and the hydrogen oxidation reaction occurs to act as the negative electrode of the power source. The product utilization rate of the electrolytic hydrogen production system is relatively high.

[0032] According to one embodiment of this application, the electrolytic hydrogen production system has a hydrogen production mode and a power generation mode;

[0033] In the hydrogen production mode, the outlet of the cathode storage is used to supply hydrogen to the hydrogen storage. When the concentration of oxidation products in the anode storage is greater than a first target value, the anode drain pipe is used to discharge the anode electrolyte in the anode storage, and the anode replenishment pipe is used to replenish the anode storage.

[0034] In the power generation mode, the hydrogen storage tank is used to supply hydrogen to the cathode chamber. When the power generation voltage is less than the second target value, the anode drain pipe is used to drain the anode electrolyte in the anode storage tank, and the anode replenishment pipe is used to replenish the anode storage tank.

[0035] According to the electrolytic hydrogen production system of this application, the hydrogen production mode is set by the electrolytic hydrogen production system. When the concentration of oxidation products in the anode storage is greater than a first target value, the anode drain pipe discharges the anode electrolyte in the anode storage, and the anode replenishment pipe replenishes the anode storage, so as to achieve continuous hydrogen production and reduce oxygen evolution. The power generation mode is set by the electrolytic hydrogen production system. When the power generation voltage is less than a second target value, the anode drain pipe discharges the anode electrolyte in the anode storage, and the anode replenishment pipe replenishes the anode storage, so as to achieve continuous power generation.

[0036] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0037] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0038] Figure 1 This is a schematic diagram of the electrolytic hydrogen production system provided in the embodiments of this application.

[0039] Figure label:

[0040] Electrolysis hydrogen production system 1000;

[0041] Electrolytic cell 100, air inlet 110 of cathode chamber, diaphragm 120, anode electrode 130, cathode electrode 140, electrode plate 150, end plate 160;

[0042] Anode reservoir 200, anode reservoir replenishment port 210, anode reservoir drain port 220;

[0043] Cathode reservoir 300, cathode reservoir outlet 310, cathode reservoir replenishment port 320;

[0044] Hydrogen storage tank 400, hydrogen storage tank outlet 410, hydrogen storage tank inlet 420;

[0045] 500mm cathode replenishment tube;

[0046] Anode replenishment tubing 600;

[0047] Anode drain pipe 700;

[0048] Pump 800;

[0049] Trachea 900. Detailed Implementation

[0050] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0051] The principle of the electrolytic hydrogen production system 1000 proposed in this application will be explained in detail below:

[0052] Among related technologies, the electrolysis hydrogen production system has high energy consumption and low safety.

[0053] To address this technical problem, this application provides an electrolytic hydrogen production system 1000, as described below. Figure 1 An electrolytic hydrogen production system 1000 according to an embodiment of this application is described.

[0054] like Figure 1 As shown, the electrolytic hydrogen production system 1000 of this application embodiment includes: an electrolyzer 100, an anode storage 200 and a cathode storage 300.

[0055] The electrolytic cell 100 includes an anode chamber and a cathode chamber.

[0056] The anode chamber and the cathode chamber are isolated from each other.

[0057] In this embodiment, the anode chamber and the cathode chamber are separated by a diaphragm 120. The diaphragm 120 can isolate or reduce the mutual penetration of electrolytic products between the anode and cathode, thereby improving the Faraday efficiency of the system.

[0058] The diaphragm 120 can be selected from anion and cation proton exchange membranes and ceramic-based composite diaphragms, etc., and no specific limitation is made in this embodiment.

[0059] In this embodiment, the electrolytic cell 100 includes an anode electrode 130, a diaphragm 120, a cathode electrode 140, an electrode plate 150, and an end plate 160.

[0060] The electrolytic cell 100 consists of an end plate 160, an electrode plate 150, an anode electrode 130, a diaphragm 120, a cathode electrode 140, an electrode plate 150, and an end plate 160, arranged from one side to the other.

[0061] The two end plates 160 are used to press and fix the electrode material and the electrode plate 150, and to maintain the fastening force required for sealing.

[0062] The negative terminal of the external power supply is connected to the cathode electrode 140 of the electrolytic cell 100, and the positive terminal of the external power supply is connected to the anode electrode 130 of the electrolytic cell 100.

[0063] The electrode 150 provides a fluid channel and enables the conduction of current, and the electrode 150 constitutes a bipolar plate.

[0064] The anode reservoir 200 is connected end to end to form a closed loop for replenishing and draining the anode chamber.

[0065] Anode reservoir 200 is used to store anolyte.

[0066] The electrolyte in the anolyte includes water-soluble redox pairs. During the electrolytic production of hydrogen, the water-soluble redox pairs undergo oxidation at the anode, without producing oxygen.

[0067] It should be noted that water-soluble redox reactions produce high-potential products after oxidation, which can be used as raw materials for power generation.

[0068] In this embodiment, a pump 800 is provided between the anode storage 200 and the anode chamber to provide power for the anode fluid.

[0069] The cathode reservoir 300 is connected end to end to form a closed loop for replenishing and draining the cathode chamber.

[0070] The cathode reservoir 300 is used to store cathode electrolyte.

[0071] In this embodiment, a pump 800 is provided between the cathode reservoir 300 and the cathode chamber to provide power for the cathode fluid.

[0072] In related technologies, hydrogen produced during the electrolysis process inevitably enters the anode through the diaphragm, causing the hydrogen content in the oxygen separator to rise. This forces the electrolytic hydrogen production system to operate only at a higher power range to generate enough oxygen to dilute the permeated hydrogen and avoid reaching the explosive limit concentration. At the same time, the oxygen evolution in the anode chamber consumes too much energy, and the generated oxygen cannot be utilized, with excessive oxygen posing a danger.

[0073] In this embodiment of the electrolytic hydrogen production system 1000, the electrolyte in the anolyte includes a water-soluble redox pair. During the electrolytic hydrogen production process, an oxidation reaction occurs. No oxygen is produced at the anode, and hydrogen is produced at the cathode.

[0074] According to the embodiment of this application, the electrolytic hydrogen production system 1000 adds a water-soluble redox pair to the anolyte of the electrolytic cell 100 to carry out an oxidation reaction during hydrogen production. No oxygen is produced at the anode, and hydrogen is produced at the cathode. This avoids the formation of an explosive gas by mixing oxygen and hydrogen, improves the safety of the electrolytic hydrogen production system 1000, expands the power operating range, and the high potential products after anode oxidation can be used as raw materials for power generation, thus improving the utilization rate of anode products.

[0075] In some embodiments, the electrolyte in the anolyte may include a halogen salt.

[0076] In the anolyte, the anions of the halogen salts are halide ions, and the cations are sodium ions, potassium ions, or hydrogen ions, etc.

[0077] The halogen ions in the anolyte can be Br. - / Br2、Br - / BrO3 - ,Br - / BrO - I - / I3 - and I - / IO3 - wait.

[0078] In this embodiment, Br is selected. - / BrO3 - , Br - It has a wide range of sources, huge reserves in seawater, and low price, and Br - / BrO3 - The redox reaction in aqueous solution is relatively rapid.

[0079] According to the embodiment of this application, the electrolytic hydrogen production system 1000 improves the safety of the system by adding a halide salt to the electrolyte in the anolyte, and the oxidation reaction of water-soluble ions occurs at the anode during electrolysis, without producing oxygen at the anode.

[0080] In some embodiments, the electrolyte in the anolyte may include bromide salts, iodide salts, hydroquinone sulfonic acid, or hydroquinone sulfonate.

[0081] When the anion of the anolyte water-soluble redox pair is a halide ion, Br can be selected. - / Br2、Br - / BrO3 - ,Br - / BrO - I - / I3 - and I - / IO3 - The cations are sodium ions, potassium ions, or hydrogen ions.

[0082] When the ions of the anolyte water-soluble redox pair are water-soluble organic compounds, hydroquinone sulfonic acid / hydroquinone sulfonate and their corresponding quinone oxidation products can be selected.

[0083] The specific types of water-soluble redox pairs can be selected according to actual usage requirements, and no specific restrictions are imposed in this embodiment.

[0084] According to the embodiment of this application, the electrolytic hydrogen production system 1000 improves the safety of the system by adding bromide salt, iodide salt, hydroquinone sulfonic acid or hydroquinone sulfonate to the electrolyte in the anolyte. During electrolysis, the oxidation reaction of water-soluble ions takes place at the anode, and no oxygen is produced at the anode.

[0085] In some embodiments, the electrolyte may include an alkali or an acid.

[0086] When the supporting electrolyte is an alkaline solution, KOH or NaOH can be used.

[0087] When the supporting electrolyte is acid, HBr or H2SO4 can be selected.

[0088] In some embodiments, the supporting electrolyte may also be other acids or bases.

[0089] According to the embodiment of this application, the electrolytic hydrogen production system 1000 generates hydrogen gas by using an electrolyte containing acid or alkali to carry out a hydrogen evolution reaction.

[0090] In some embodiments, such as Figure 1 As shown, the anode electrode 130 of the electrolytic cell 100 may include at least one of carbon fiber, graphite, titanium, and boron-doped diamond.

[0091] The anode electrode 130 of the electrolytic cell 100 can be selected from one of carbon fiber, graphite, titanium, or boron-doped diamond, or a combination of several of them.

[0092] In this embodiment, the anode electrode 130 of the electrolytic cell 100 is made of boron-doped diamond. The boron-doped diamond electrode has a high oxygen evolution potential, which makes it difficult for the oxygen evolution reaction to occur.

[0093] According to the embodiment of this application, the electrolytic hydrogen production system 1000 reduces the occurrence of oxygen evolution reaction at the anode by selecting at least one of carbon fiber, graphite, titanium, and boron-doped diamond as the anode electrode 130.

[0094] In some embodiments, such as Figure 1 As shown, the cathode electrode 140 of the electrolyzer 100 may include at least one of a carbon-supported platinum catalyst and a nickel-hydrogen battery negative electrode hydrogen storage alloy.

[0095] The cathode electrode 140 of the electrolyzer 100 can be one of a carbon-supported platinum catalyst and a nickel-metal hydride battery anode hydrogen storage alloy, or a combination of a carbon-supported platinum catalyst and a nickel-metal hydride battery anode hydrogen storage alloy.

[0096] Electrolyzer 100, which uses a carbon-supported platinum catalyst or a nickel-metal hydride battery negative electrode hydrogen storage alloy material, can simultaneously have the ability to produce hydrogen and oxidize hydrogen.

[0097] It should be noted that the electrolyzer 100 uses a cathode electrode 140 with hydrogen oxidation capability, which can act as the negative electrode of the power source when there is no energy input to the electrolysis hydrogen production system 1000 and the electrolysis hydrogen production system 1000 needs to generate electricity.

[0098] According to the embodiments of this application, the electrolytic hydrogen production system 1000 can have both electrolytic hydrogen production and power generation capabilities by selecting at least one of carbon-supported platinum catalyst and nickel-hydrogen battery negative electrode hydrogen storage alloy as the cathode electrode 140.

[0099] In some embodiments, such as Figure 1 As shown, the cathode electrode 140 of the electrolytic cell 100 may include at least one of Raney nickel catalyst and nickel-molybdenum alloy catalyst.

[0100] The cathode electrode 140 of the electrolytic cell 100 can be one of Raney nickel catalyst and nickel-molybdenum alloy catalyst, or a combination of Raney nickel catalyst and nickel-molybdenum alloy catalyst.

[0101] The cathode electrode 140 of the electrolyzer 100, which uses Raney nickel catalyst and nickel-molybdenum alloy catalyst, has the ability to evolve hydrogen.

[0102] According to the embodiments of this application, the electrolytic hydrogen production system 1000 can have the ability to produce hydrogen by selecting at least one of Raney nickel catalyst and nickel-molybdenum alloy catalyst as cathode electrode 140.

[0103] In some embodiments, such as Figure 1 As shown, the electrolytic hydrogen production system 1000 may further include: a hydrogen storage tank 400, a cathode replenishment pipe 500, an anode replenishment pipe 600, and an anode drain pipe 700.

[0104] The hydrogen storage unit 400 is connected to the outlet 310 of the cathode storage unit.

[0105] In this embodiment, the cathode storage 300 is used to separate the hydrogen and liquid mixture, and the cathode storage 300 has a gas pipe 900 connected to the gas inlet 420 of the hydrogen storage.

[0106] The cathode replenishment pipe 500 is connected to the replenishment port 320 of the cathode storage device. The cathode replenishment pipe 500 is used to replenish the water required for electrolytic hydrogen production and maintain a stable liquid level.

[0107] The anode replenishment pipe 600 is connected to the replenishment port 210 of the anode storage tank. In hydrogen production mode, the anode replenishment pipe 600 is used to replenish fresh bromide ions to maintain an appropriate bromide ion concentration. In power generation mode, the anode replenishment pipe 600 is used to replenish bromate ions generated during electrolytic hydrogen production from an external storage tank.

[0108] The anode drain pipe 700 is connected to the drain port 220 of the anode storage tank. In hydrogen production mode and power generation mode, the anode drain pipe 700 is used to discharge the mixed solution with a high bromate concentration to maintain an appropriate electrolysis voltage. The liquid discharged from the anode drain pipe 700 enters the external storage tank.

[0109] According to the embodiment of this application, the electrolytic hydrogen production system 1000 stores the hydrogen produced by electrolytic hydrogen production through a hydrogen storage tank 400, replenishes the cathode storage tank 300 with water required for electrolytic hydrogen production through a cathode replenishment pipe 500, replenishes the anode storage tank 200 with bromide ions or bromate ions through an anode replenishment pipe 600, and discharges the mixed liquid with a high bromate concentration from the anode storage tank 200 through an anode drain pipe 700, thereby maintaining the continuous electrolytic hydrogen production and power generation capabilities of the electrolytic hydrogen production system 1000.

[0110] In some embodiments, the electrolysis hydrogen production system 1000 may have a hydrogen production mode.

[0111] In hydrogen production mode, the outlet 310 of the cathode storage is used to supply hydrogen to the hydrogen storage 400. When the concentration of oxidation products in the anode storage 200 is greater than the first target value, the anode drain pipe 700 is used to drain the anode electrolyte in the anode storage 200, and the anode replenishment pipe 600 is used to replenish the anode storage 200.

[0112] It should be noted that the oxidation product in this embodiment is bromate ions. The first target value is the set bromate ion concentration. As the concentration of bromate ions increases, the electrolysis voltage of the electrolytic hydrogen production system 1000 continuously increases. In order to avoid the electrolysis voltage being too high and causing water decomposition to produce oxygen, the anode drain pipe 700 discharges the anode electrolyte in the anode storage tank 200, and the anode replenishment pipe 600 replenishes the anode storage tank 200.

[0113] According to the embodiment of this application, the electrolytic hydrogen production system 1000 is set to a hydrogen production mode. When the concentration of oxidation products in the anode storage 200 is greater than a first target value, the anode drain pipe 700 discharges the anode electrolyte in the anode storage 200, and the anode replenishment pipe 600 replenishes the anode storage 200 to achieve continuous hydrogen production and reduce oxygen evolution.

[0114] In some embodiments, such as Figure 1 As shown, the hydrogen storage device 400 may include an outlet, and the cathode chamber may include an inlet.

[0115] The outlet 410 of the hydrogen storage tank is connected to the inlet 110 of the cathode chamber via a gas pipe 900.

[0116] It should be noted that when there is no energy input to the electrolytic hydrogen production system 1000 and the electrolytic hydrogen production system 1000 needs to generate electricity, the gas in the hydrogen storage tank 400 enters the cathode chamber through the gas pipe 900, and the hydrogen oxidation reaction occurs, which acts as the negative electrode of the power source.

[0117] According to the embodiment of this application, the electrolytic hydrogen production system 1000 connects the outlet 410 of the hydrogen storage tank to the inlet 110 of the cathode chamber, so that the gas from the hydrogen storage tank 400 can enter the cathode chamber through the gas pipe 900 and undergo a hydrogen oxidation reaction to act as the negative electrode of the power supply. The product utilization rate of the electrolytic hydrogen production system 1000 is high.

[0118] In some embodiments, the electrolytic hydrogen production system 1000 may have a hydrogen production mode and a power generation mode.

[0119] In hydrogen production mode, the outlet 310 of the cathode storage is used to supply hydrogen to the hydrogen storage 400. When the concentration of oxidation products in the anode storage 200 is greater than the first target value, the anode drain pipe 700 is used to drain the anode electrolyte in the anode storage 200, and the anode replenishment pipe 600 is used to replenish the anode storage 200.

[0120] In this embodiment, the oxidation product is bromate ions, and the first target value is the set bromate ion concentration. As the concentration of bromate ions increases, the electrolysis voltage of the electrolytic hydrogen production system 1000 continuously increases. In order to avoid the electrolysis voltage being too high and causing water decomposition to produce oxygen, the anode drain pipe 700 discharges the anode electrolyte in the anode storage tank 200, and the anode replenishment pipe 600 replenishes the anode storage tank 200.

[0121] In power generation mode, hydrogen storage tank 400 is used to supply hydrogen to the cathode chamber. When the power generation voltage is less than the second target value, anode drain pipe 700 is used to drain the anode electrolyte in anode storage tank 200, and anode replenishment pipe 600 is used to replenish the anode storage tank 200.

[0122] In this embodiment, when the power generation voltage drops significantly, bromate ions generated during hydrogen electrolysis can be replenished from the external storage tank through the anode replenishment pipe 600 and circulated back to the external storage tank through the anode drain pipe 700 to maintain liquid level balance and ensure the system's ability to continuously generate electricity.

[0123] According to the embodiment of this application, the electrolytic hydrogen production system 1000 is set to a hydrogen production mode. When the concentration of oxidation products in the anode storage 200 is greater than a first target value, the anode drain pipe 700 discharges the anode electrolyte in the anode storage 200, and the anode replenishment pipe 600 replenishes the anode storage 200 to achieve continuous hydrogen production and reduce oxygen evolution. The electrolytic hydrogen production system 1000 is also set to a power generation mode. When the power generation voltage is less than a second target value, the anode drain pipe 700 discharges the anode electrolyte in the anode storage 200, and the anode replenishment pipe 600 replenishes the anode storage 200 to achieve continuous power generation.

[0124] In some embodiments, such as Figure 1As shown, the electrolytic cell 100 forms an isolated anode chamber and a cathode chamber through a diaphragm 120. The anode reservoir 200 is connected end-to-end to the anode chamber. The electrolyte in the anode electrolyte includes bromide salts. The cathode reservoir 300 is connected end-to-end to the cathode chamber. The medium in the anode electrolyte includes NaOH. The anode electrode 130 of the electrolytic cell 100 is a boron-doped diamond electrode. The cathode electrode 140 of the electrolytic cell 100 is a hydrogen storage alloy for hydrogen batteries. The hydrogen reservoir 400 is connected to the outlet 310 of the cathode reservoir. The cathode replenishment pipe 500 is connected to the replenishment port 320 of the cathode reservoir. The anode replenishment pipe 600 is connected to the replenishment port 210 of the anode reservoir. The anode drain pipe 700 is connected to the drain port 220 of the anode reservoir.

[0125] In this embodiment, the anion of the bromide salt is Br. - / BrO3 - .

[0126] It should be noted that bromide ions are widely available, abundant in seawater, and relatively inexpensive. - / BrO3 - The oxidation-reduction reaction in aqueous solution is relatively rapid, and sodium bromide has a high solubility in water, exceeding 2 mol / L, with an energy density exceeding 100 Wh / kg. Compared to organic systems, aqueous anodic electrochemical reactions offer higher safety. Bromine ions are also excellent flame retardants, reducing the risk of system fires. Furthermore, the reaction between bromine and hydrogen is difficult, and even if they mix, an explosion is unlikely. Moreover, the electrocatalytic oxidation of bromide ions under alkaline conditions does not easily produce volatile bromine gas.

[0127] When an external energy input of 100 kW is supplied to the electrolytic cell, and the supporting electrolyte is NaOH, assuming a pH of 14, a hydrogen evolution reaction occurs in the cathode chamber: 2H₂O + 2e⁻. - =2OH - +H2(-0.82V SHE), bromide ion oxidation occurs in the anolyte, Br - +6OH - =BrO3 - +3H2O+6e - (0.61V SHE).

[0128] In this embodiment, the theoretical electrolysis voltage is 1.43V. When the input voltage is higher than 1.43V, hydrogen gas is generated in the cathode chamber of the electrolytic cell 100. After the gas-liquid mixture of hydrogen gas and sodium hydroxide aqueous solution enters the cathode storage 300, most of the hydrogen gas separates from the liquid under the action of gravity and enters the hydrogen storage 400 through the gas pipe 900. The remaining sodium hydroxide solution is recycled.

[0129] The cathode replenishment tube 500 replenishes the water required for hydrogen electrolysis and maintains a stable liquid level. The anode uses a boron-doped diamond electrode with low oxygen evolution activity, and the solution pH is adjusted to minimize oxygen production during the anolyte reaction.

[0130] Before starting the machine, nitrogen is used to replace the air above the liquid surface in the anode storage tank 200. Even if a small amount of hydrogen passes through the diaphragm 120 into the anode storage tank 200, the anode storage tank 200 will only contain nitrogen and hydrogen gases, and there is no risk of explosion.

[0131] During electrolysis, bromide ions at the anode are continuously oxidized to bromate ions. As the concentration of bromate ions increases, the electrolysis voltage of the hydrogen production system 1000 continuously rises. To prevent excessively high electrolysis voltage from causing water decomposition and oxygen production, fresh bromide ions are added through the anode replenishment pipe 600 to maintain an appropriate bromide ion concentration. Meanwhile, a mixture with a high bromate ion concentration is discharged through the anode drain pipe 700 to maintain an appropriate electrolysis voltage. The liquid discharged through the anode drain pipe 700 enters an external storage tank, allowing the hydrogen production system 1000 to continuously produce hydrogen. This system has good power adaptability, eliminates the risk of hydrogen and oxygen gas mixing, and ensures high safety.

[0132] It should be noted that the size of the external storage tank can be selected according to the capacity required for power generation and hydrogen production, so as to achieve continuous hydrogen production and power generation.

[0133] When there is no energy input to the electrolytic hydrogen production system 1000 and the electrolytic hydrogen production system 1000 needs to generate electricity, the gas in the hydrogen storage tank 400 enters the cathode chamber of the electrolytic cell 100 through the gas pipe 900, where a hydrogen oxidation reaction occurs, which acts as the negative electrode of the power source. Meanwhile, the sodium bromate solution at the anode undergoes a reduction reaction to generate sodium bromide solution.

[0134] The open-circuit voltage of a single chamber in electrolytic cell 100 is 1.43V. Bromate ions are reduced to bromide ions, while hydrogen is oxidized to produce water, generating current. When the power generation voltage drops significantly, bromate ions generated during hydrogen electrolysis can be replenished from an external storage tank through the anode replenishment pipe 600, and the bromate ions can be circulated back to the external storage tank through the anode drain pipe 700 to maintain liquid level balance and ensure the system's continuous power generation capability.

[0135] According to the electrolytic hydrogen production system 1000 provided in the embodiments of this application, a water-soluble redox coupler Br is added to the anolyte of the electrolytic cell 100. - / BrO3 -During the electrolytic hydrogen production process, an oxidation reaction is carried out. No oxygen is produced at the anode, while hydrogen is produced at the cathode. This avoids the formation of explosive gases from the mixing of oxygen and hydrogen, thus improving the safety of the 1000 electrolytic hydrogen production system and expanding its power operating range. At the same time, the high-potential products after anode oxidation can be used as raw materials for power generation through reduction reactions, thereby improving the utilization rate of anode products.

[0136] The terms "first," "second," etc., used in the specification and claims of this application are used to distinguish similar objects and not to describe a specific order or sequence. It should be understood that such use of data can be interchanged where appropriate so that embodiments of this application can be implemented in orders other than those illustrated or described herein, and the objects distinguished by "first," "second," etc., are generally of the same class and the number of objects is not limited; for example, a first object can be one or more. Furthermore, in the specification and claims, "and / or" indicates at least one of the connected objects, and the character " / " generally indicates that the preceding and following objects are in an "or" relationship.

[0137] In the description of this application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., indicating the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application.

[0138] In the description of this application, "first feature" and "second feature" may include one or more of the features.

[0139] In the description of this application, "multiple" means two or more.

[0140] In the description of this application, the first feature being "above" or "below" the second feature may include the first and second features being in direct contact, or the first and second features being in contact through another feature between them.

[0141] In the description of this application, the terms "above," "over," and "on top" for the first feature and the second feature include the first feature being directly above or diagonally above the second feature, or simply indicate that the first feature is at a higher horizontal level than the second feature.

[0142] Other configurations of the embodiments of this application, such as ... and ..., and operations, are known to those skilled in the art and will not be described in detail here.

[0143] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0144] Although embodiments of this application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of this application, the scope of which is defined by the claims and their equivalents.

Claims

1. An electrolytic hydrogen production system, characterized in that, include: The electrolytic cell forms isolated anode and cathode chambers; An anode storage container, connected end-to-end to the anode chamber, is used to store the anolyte, wherein the electrolyte in the anolyte includes a water-soluble redox pair; A cathode reservoir, connected end-to-end to the cathode chamber, is used to store cathode electrolyte.

2. The electrolytic hydrogen production system according to claim 1, characterized in that, The electrolyte in the anolyte includes a halogen salt.

3. The electrolytic hydrogen production system according to claim 1, characterized in that, The electrolyte in the anolyte includes bromide salts, iodide salts, hydroquinone sulfonic acid, or hydroquinone sulfonate.

4. The electrolytic hydrogen production system according to claim 1, characterized in that, The electrolyte contains acid or alkali.

5. The electrolytic hydrogen production system according to claim 1, characterized in that, The anode electrode of the electrolytic cell includes at least one of carbon fiber, graphite, titanium, and boron-doped diamond.

6. The electrolytic hydrogen production system according to claim 1, characterized in that, The cathode electrode of the electrolyzer includes at least one of a carbon-supported platinum catalyst and a nickel-hydrogen battery negative electrode hydrogen storage alloy.

7. The electrolytic hydrogen production system according to claim 1, characterized in that, The cathode electrode of the electrolytic cell includes at least one of Raney nickel catalyst and nickel-molybdenum alloy catalyst.

8. The electrolytic hydrogen production system according to any one of claims 1-7, characterized in that, Also includes: A hydrogen storage device is connected to the outlet of the cathode storage device; A cathode replenishment pipe is connected to the replenishment port of the cathode reservoir; An anode replenishment pipe is connected to the replenishment port of the anode reservoir; The anode drain pipe is connected to the drain port of the anode reservoir.

9. The electrolytic hydrogen production system according to claim 8, characterized in that, The electrolytic hydrogen production system has a hydrogen production mode; In the hydrogen production mode, the outlet of the cathode storage is used to supply hydrogen to the hydrogen storage. When the concentration of oxidation products in the anode storage is greater than a first target value, the anode drain pipe is used to drain the anode electrolyte in the anode storage, and the anode replenishment pipe is used to replenish the anode storage.

10. The electrolytic hydrogen production system according to claim 8, characterized in that, The outlet of the hydrogen storage device is connected to the inlet of the cathode chamber.

11. The electrolytic hydrogen production system according to claim 10, characterized in that, The electrolysis hydrogen production system has a hydrogen production mode and a power generation mode; In the hydrogen production mode, the outlet of the cathode storage is used to supply hydrogen to the hydrogen storage. When the concentration of oxidation products in the anode storage is greater than a first target value, the anode drain pipe is used to discharge the anode electrolyte in the anode storage, and the anode replenishment pipe is used to replenish the anode storage. In the power generation mode, the hydrogen storage tank is used to supply hydrogen to the cathode chamber. When the power generation voltage is less than the second target value, the anode drain pipe is used to drain the anode electrolyte in the anode storage tank, and the anode replenishment pipe is used to replenish the anode storage tank.

Images