An electrically controlled reversible micro hydrogen release box for hydrogen reference electrode hydrogen supply

Abstract

The present application belongs to the technical field of electrochemical hydrogen storage and release, and particularly relates to an electrically controlled reversible micro hydrogen release box for hydrogen supply of a hydrogen reference electrode, comprising a sealed shell assembly, a power supply and a hydrogen reaction device; the hydrogen reaction device comprises a first unit, a second unit and a proton film, and a sealed micro gas cavity is arranged between the proton film and the first unit; the present application has three modes; when hydrogen is released, the proton film is soaked by ultrapure water, the first unit serves as an anode, the second unit serves as a cathode, hydrogen protons pass through the proton film to reach the second unit to form hydrogen gas by obtaining electrons; when hydrogen is stored, the polarity is switched, the first unit serves as a cathode, the second unit serves as an anode, water molecules in the second unit are converted into hydrogen protons and pass through the proton film to reach the first unit, combine with electrons and enter a hydrogen storage material to complete hydrogen storage; when hydrogen is stored, the micro gas cavity separates the hydrogen proton conduction path. The present application realizes reversible hydrogen storage and release, power-off hydrogen locking and non-pole adjustment of the amount of released hydrogen by polarity switching and current control, there is no free flowing liquid in the hydrogen release box, and the hydrogen release box can be recycled and reused.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical hydrogen storage and release technology, and particularly relates to an electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode. Background Technology

[0002] Reversible hydrogen reference electrodes have become a core reference electrode in the field of electrocatalysis testing due to their lack of liquid junction potential, wide pH adaptability, and absence of ion contamination. However, the stable operation of reversible hydrogen reference electrodes is highly dependent on a long-term, trace, and controllable supply of hydrogen.

[0003] Currently, traditional hydrogen storage alloys do not contain hydrogen and require external hydrogen activation to release hydrogen, making them unsuitable for direct use as sealed micro hydrogen sources. Furthermore, the passive hydrogen release of pure alloys cannot be shut off, resulting in continuous hydrogen leakage, which makes them unsuitable for the stringent requirements of steady-state hydrogen supply in precision electrochemical testing.

[0004] The hydrogen release boxes used with commercial reversible hydrogen reference electrodes are all passive, current-limiting, disposable structures that lack electronic start-stop and cyclic storage functions. They have a fixed lifespan and cannot be reused. In addition, the high cost of imports severely restricts the independent development of domestic reversible hydrogen reference electrode systems.

[0005] Furthermore, the hydrogen release structure in traditional nickel-hydrogen systems uses a fully liquid electrolyte, which must be immersed in the liquid for use. This results in inherent defects such as leakage, ion contamination, and the inability to seal and miniaturize, making it difficult to apply to hydrogen reference electrode conditions in open air environments.

[0006] Therefore, there is an urgent need for an electrically controlled reversible micro hydrogen release cell for supplying hydrogen to a hydrogen reference electrode. Summary of the Invention

[0007] The purpose of this invention is to provide an electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode, so as to solve the above-mentioned problems.

[0008] To achieve the above objectives, the present invention provides the following solution: An electrically controlled reversible miniature hydrogen release box for supplying hydrogen to a hydrogen reference electrode includes: A sealed housing assembly, and a power supply and a hydrogen reaction device disposed within the sealed housing assembly, the hydrogen reaction device being connected to the power supply; The power supply can switch polarity; The hydrogen reaction device includes a first unit, a second unit, and a proton exchange membrane disposed between the two, with a sealed micro-gas chamber provided between the proton exchange membrane and the first unit; The first unit includes a hydrogen storage material, and the sealed micro-cavity is disposed between the hydrogen storage material and the proton exchange membrane; The hydrogen reactor has a hydrogen release mode, a hydrogen storage mode, and a hydrogen preservation mode; When the hydrogen reaction device is in the hydrogen release mode, after the proton membrane is wetted with ultrapure water, the first unit acts as the anode and the second unit acts as the cathode, causing the hydrogen atoms in the hydrogen storage material to lose electrons and become hydrogen protons, which then pass through the proton membrane to reach the second unit and gain electrons to form hydrogen gas. When the hydrogen reaction device is in the hydrogen storage mode, after the proton membrane is wetted with ultrapure water, the first unit acts as the cathode and the second unit acts as the anode, causing the water molecules in the second unit to be converted into hydrogen protons and pass through the proton membrane to reach the first unit. The hydrogen protons combine with electrons and enter the hydrogen storage material to complete hydrogen storage. When the hydrogen reactor is in storage mode, both the first unit and the second unit are disconnected from the power supply, and the sealed micro-gas cavity blocks the electron conduction path.

[0009] Optionally, the sealed housing assembly includes an upper cover and a lower cover, the upper cover and the lower cover being fixedly disposed, the power supply being disposed inside the upper cover, and the hydrogen reaction device being disposed inside the lower cover.

[0010] Optionally, the first unit further includes a dense graphite current collector fixed to one end of the hydrogen storage material, the dense graphite current collector being fixed to one end of the upper cover; The dense graphite current collector is connected to the power source.

[0011] Optionally, the second unit includes a platinum-plated titanium mesh, which is in contact with the side of the proton membrane away from the micro-cavity spacer; It also includes a porous graphite current collector, which is fixed inside the lower cover and in contact with the platinum-plated titanium mesh; The porous graphite current collector is connected to the power source; When the hydrogen reaction device is in the hydrogen release mode, the platinum-plated titanium mesh acts as a cathode, causing hydrogen protons to gain electrons on its surface to generate hydrogen gas. When the hydrogen reactor is in the hydrogen storage mode, the platinum-plated titanium mesh acts as the anode, causing ultrapure water to lose electrons on its surface to generate oxygen and hydrogen protons. The lower cover is provided with multiple through holes, which are used for gas discharge or for ultrapure water replenishment.

[0012] Optionally, the power source includes a battery, the polarity of which can be switched by flipping the battery.

[0013] Optionally, it may also include an adjustment device connected to the power supply, the adjustment device being used to adjust the current of the power supply.

[0014] Optionally, the adjustment device includes a sliding rheostat, and the first unit and the second unit are connected to the power supply through the sliding rheostat; The movable end of the sliding rheostat is connected to a hydrogen flow control disk, which is rotatably engaged with the upper cover. The fixed end of the sliding rheostat is fixed inside the upper cover.

[0015] Optionally, a switch is provided between the sliding rheostat and the power supply.

[0016] Optionally, a fluororubber insulating sealing ring is provided between the proton exchange membrane and the hydrogen storage material, and the fluororubber insulating sealing ring, the proton exchange membrane and the hydrogen storage material together form the sealed micro-gas cavity.

[0017] Optionally, the hydrogen storage material is molded from 100-300 mesh hydrogen storage material powder under a molding pressure of 5-10 MPa.

[0018] Compared with the prior art, the present invention has the following advantages and technical effects: The electrically controlled reversible micro hydrogen release box provided by this invention adopts a semi-solid design, containing only ultrapure water in the pores of the proton exchange membrane, with no free-flowing liquid, completely eliminating the risk of leakage and ion contamination. It can directly supply hydrogen to the reversible hydrogen reference electrode in an open air environment. By switching the power polarity, the same device can achieve both hydrogen release and hydrogen storage reversible modes. Once the hydrogen storage material is depleted, it does not need to be replaced; it can be electrochemically recharged and reused in situ, significantly reducing operating costs. In hydrogen release mode, the hydrogen flow rate is linearly proportional to the operating current, and can be precisely steplessly adjusted within the range of 0.5-10 μL / min via an adjustment device. After power failure, the micro-cavity cuts off the hydrogen proton conduction pathway, and the self-release rate approaches zero, achieving long-term sealed storage. In hydrogen storage mode, only a small amount of ultrapure water needs to be added and voltage applied to complete hydrogen recharging, making operation simple. The overall structure adopts a partitioned sealing design with upper and lower covers, and a quadruple sealing structure ensures no significant hydrogen loss during 6-8 months of power-off storage. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly described below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Figure 1 This is a schematic diagram of the structure of the present invention; Figure 2 This is a schematic diagram illustrating the working principle of the hydrogen release mode of this invention; Figure 3 This is a schematic diagram illustrating the working principle of the hydrogen storage mode of the present invention. Among them, 1. Hydrogen flow control disk; 2. Switch; 3. Brush ring; 4. Sliding rheostat; 5. Battery; 7. Top cover; 8. Bottom cover; 9. Dense graphite current collector; 10. Hydrogen storage material; 11. Fluororubber insulating sealing ring; 12. Proton exchange membrane; 13. Platinum-plated titanium mesh; 14. Porous graphite current collector. Detailed Implementation

[0020] 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.

[0021] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0022] Reference Figures 1 to 3 This invention discloses an electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode, comprising: A sealed housing assembly, and a power supply and a hydrogen reactor disposed within the sealed housing assembly, the hydrogen reactor being connected to the power supply; The power supply polarity can be switched; The hydrogen reactor includes a first unit, a second unit, and a proton exchange membrane 12 disposed between the two. A sealed micro-gas chamber is provided between the proton exchange membrane 12 and the first unit. The first unit includes a hydrogen storage material 10, and a sealed micro-gas cavity is disposed between the hydrogen storage material 10 and the proton membrane 12. The hydrogen reactor has a hydrogen release mode, a hydrogen storage mode, and a preservation mode; When the hydrogen reactor is in hydrogen release mode, after the proton exchange membrane 12 is wetted with ultrapure water, the first unit acts as the anode and the second unit acts as the cathode, causing the hydrogen atoms in the hydrogen storage material 10 to lose electrons and become hydrogen protons, which then pass through the proton exchange membrane 12 to reach the second unit to obtain electrons and form hydrogen gas. When the hydrogen reactor is in hydrogen storage mode, after the proton exchange membrane 12 is wetted with ultrapure water, the first unit acts as the cathode and the second unit acts as the anode, causing the water molecules in the second unit to be converted into hydrogen protons and pass through the proton exchange membrane 12 to reach the first unit. The hydrogen protons combine with electrons and enter the hydrogen storage material 10 to complete hydrogen storage. When the hydrogen reactor is in storage mode, both the first and second units are disconnected from the power supply, and the sealed micro-gas chamber blocks the hydrogen proton conduction path.

[0023] In operation, in hydrogen release mode, the proton exchange membrane 12 is wetted with ultrapure water. The first unit acts as the anode, and the second unit as the cathode. Hydrogen atoms in the hydrogen storage material 10 lose electrons and become hydrogen protons. These protons pass through the proton exchange membrane 12 to reach the second unit, where they gain electrons to generate hydrogen gas. In hydrogen storage mode, the power supply polarity is switched, with the first unit becoming the cathode and the second unit as the anode. Water molecules in the second unit transform into hydrogen protons and pass through the proton exchange membrane 12 to reach the first unit. The protons combine with electrons and enter the hydrogen storage material 10 to complete hydrogen storage. In preservation mode, because the external auxiliary power supply is disconnected, the hydrogen atoms at the anode do not have an externally applied voltage or current and cannot detach from the hydrogen storage material, thus achieving long-term stable preservation.

[0024] As an optional implementation, the sealed housing assembly includes an upper cover 7 and a lower cover 8, which are fixedly disposed. The power supply is disposed inside the upper cover 7, and the hydrogen reaction device is disposed inside the lower cover 8.

[0025] The top and bottom partition layout physically isolates the circuit control from the electrochemical reaction, preventing liquids or gases from corroding electronic components. The structure is compact and facilitates miniaturization and integration.

[0026] As an optional implementation, the first unit also includes a dense graphite current collector 9 fixed to one end of the hydrogen storage material 10, and the dense graphite current collector 9 is fixed to one end of the upper cover 7. The dense graphite current collector 9 is connected to the power supply.

[0027] The dense graphite current collector 9 distributes the current evenly to the surface of the hydrogen storage material 10. Its dense structure isolates gas and water vapor, while providing mechanical support and uniform conductivity.

[0028] As an optional implementation, the second unit includes a platinum-plated titanium mesh 13, which is in contact with the side of the proton membrane 12 away from the micro-cavity spacer. It also includes a porous graphite current collector 14, which is fixed inside the lower cover 8 and in contact with the platinum-plated titanium mesh 13. The porous graphite current collector 14 is connected to the power supply; When the hydrogen reactor is in hydrogen release mode, the platinum-plated titanium mesh 13 serves as the cathode, allowing hydrogen protons to gain electrons on its surface to generate hydrogen gas. When the hydrogen reactor is in hydrogen storage mode, the platinum-plated titanium mesh 13 acts as the anode, causing ultrapure water to lose electrons on its surface to generate oxygen and hydrogen protons. The lower cover 8 has multiple through holes for gas discharge or for replenishing ultrapure water.

[0029] The second unit includes a platinum-titanium coated mesh 13, which contacts the side of the proton exchange membrane 12 away from the micro-gas chamber. A porous graphite current collector 14 is fixed inside the lower cover 8 and contacts the platinum-titanium coated mesh 13; the porous graphite current collector 14 is connected to a power source. In hydrogen release mode, the platinum-titanium coated mesh 13 acts as a cathode, catalyzing the generation of hydrogen gas from hydrogen protons; in hydrogen storage mode, it acts as an anode, catalyzing the generation of oxygen and hydrogen protons from water. Multiple through-holes are provided on the lower cover 8, corresponding to the platinum-titanium coated mesh 13, for gas exhaust or ultrapure water replenishment.

[0030] As an alternative implementation, the power source includes a battery 5, the polarity of which is switched by flipping the battery 5.

[0031] The polarity is switched by mechanically reversing the polarity of the battery 5. This method is simple and reliable, requires no electronic switch, and users can switch between hydrogen release and hydrogen storage modes simply by removing the battery and reversing its installation.

[0032] As an optional implementation, an adjustment device is also included, which is connected to a power supply and is used to adjust the current of the power supply.

[0033] By adjusting the current magnitude to linearly control the hydrogen production rate, the problem of fixed flow rate in passive hydrogen release boxes can be solved to match the requirements of different reference electrodes.

[0034] As an optional implementation, the adjustment device includes a sliding rheostat 4, and the first unit and the second unit are connected to the power supply through the sliding rheostat 4. The movable end of the sliding rheostat 4 is connected to the hydrogen flow control disk 1, which is rotatably engaged with the upper cover 7. The fixed end of the sliding rheostat 4 is fixed inside the upper cover 7.

[0035] The regulating device includes a sliding rheostat 4. The first unit and the second unit are connected to the power supply through the sliding rheostat 4. The movable end of the sliding rheostat 4 is connected to the hydrogen flow control disk 1. The disk is rotatably engaged with the upper cover 7, and the fixed end of the resistor is fixed inside the upper cover 7. The user rotates the disk to change the resistance value, thereby adjusting the current and achieving precise control of the hydrogen flow.

[0036] As an optional implementation, a switch 2 is provided between the sliding rheostat 4 and the power supply.

[0037] The movable end of the sliding rheostat 4 is matched with the limit of the switch 2. A protruding structure is provided below the switch 2. The movable end of the sliding rheostat 4 is matched with the limit of the protruding structure. The protruding structure can conduct electricity and also drive the movable end of the sliding rheostat 4 to slide.

[0038] The switch 2 is designed in a square shape and nested with the hydrogen flow control disk 1 above it. Rotating the hydrogen flow control disk 1 will cause the switch 2 to rotate. The lower protrusion of the switch 2 will cause the movable end of the sliding rheostat 4 to slide.

[0039] Switch 2 uses a brush to connect to the power supply, avoiding the problem of wire tangling caused by rotation.

[0040] Switch 2 controls the start and stop of the circuit. Pressing it activates the circuit and generates hydrogen instantly. Disconnecting it immediately stops hydrogen release, meeting the requirements for rapid response and preventing hydrogen leakage.

[0041] As an optional implementation, a fluororubber insulating sealing ring 11 is provided between the proton exchange membrane 12 and the hydrogen storage material 10, and the fluororubber insulating sealing ring 11, the proton exchange membrane 12 and the hydrogen storage material 10 together form a closed micro-gas cavity.

[0042] The fluororubber insulating sealing ring 11, the proton membrane 12, and the hydrogen storage material 10 together form a closed micro-cavity. Water vapor can diffuse and conduct protons within the closed micro-cavity, providing a working basis for hydrogen storage mode and hydrogen release mode. At the same time, when in storage mode, the closed micro-cavity will always be kept moist, providing conditions for rapid release of hydrogen during operation.

[0043] As an optional implementation, the hydrogen storage material 10 is molded from 100-300 mesh hydrogen storage material powder under a molding pressure of 5-10 MPa.

[0044] The particle size and pressure ensure that the pressed electrode has sufficient strength and appropriate porosity, preventing hydrogen pulverization during charging and discharging, and ensuring good electrical contact with the current collector.

[0045] The following is a detailed description of the present invention: Sealed housing assembly: Made of electrochemical grade PEEK material, consisting of an upper cover 7 and a lower cover 8, which are sealed and fixed, preferably by compression, and anaerobic sealant is applied to the gaps to achieve permanent airtightness.

[0046] The bottom of the lower cover 8 has 1-3 0.2mm through holes, and the cathode interface is integrated on the side of the lower cover 8. The upper cover 7 is a composite structure. The lower side of the upper cover 7 is used to fasten with the lower cover 8, and the upper side of the upper cover 7 has a power post and is used to integrate the battery 5, the sliding rheostat 4, the switch 2 and the brush ring 3. The overall withstand voltage range is 0-0.6MPa.

[0047] The upper cover 7 and the lower cover 8 form a physically isolated electrical cavity and hydrogen reaction device cavity. The wiring harness passage inside the upper cover 7 is also sealed to ensure the isolation effect.

[0048] The hydrogen reaction apparatus includes a first unit, a second unit, a proton exchange membrane 12, etc.

[0049] The first unit consists of a dense graphite current collector 9 and a hydrogen storage material 10. The hydrogen storage material 10 is preferably a powder sheet of ZrNi5 alloy, etc. The dense graphite current collector 9 is attached to the bottom of the upper cover 7, and the electrodes of the hydrogen storage material 10 are pressed tightly against the surface of the dense graphite current collector 9 to achieve uniform conductivity and hydrogen storage.

[0050] The second unit includes a platinum-titanium mesh 13 with PTFE embedded at the edges and a porous graphite current collector 14. The platinum-titanium mesh 13 is attached to the lower surface of the proton exchange membrane 12 to realize proton catalytic gas production and electron export. At the same time, the PTFE embedded at the edges presses the proton exchange membrane to prevent gaps between layers, thereby playing a role in interlayer sealing.

[0051] The proton exchange membrane 12 can be a Nafion membrane, a trifluorostyrene copolymer membrane, etc. When selecting the proton exchange membrane 12, it should be selected that easily generates H under energization. + Furthermore, it is not easy to generate H under normal temperature and pressure conditions. + Hydrogen storage materials.

[0052] A closed micro-cavity is formed between the proton exchange membrane 12 and the hydrogen storage material 10 through a fluororubber insulating sealing ring 11, and the two do not have direct hard contact. In the working state, the saturated water vapor on the surface of the proton exchange membrane 12 and the humid atmosphere in the closed micro-cavity form a hydrated proton conduction medium, and hydrogen protons can diffuse across the gap through the gas phase humid environment to ensure the normal conduction of the electrochemical circuit. In the static state, the non-contact structure completely cuts off the micro-electronic conduction path at the interface, eliminates the spontaneous hydrogen evolution reaction of the galvanic cell, and realizes long-term sealing of the hydrogen storage material.

[0053] Both the first and second units use lead-out electrode wires that pass through the sealed housing assembly and are sealed to ensure zero air leakage and insulation sealing.

[0054] It also includes battery 5, which uses a high-capacity button cell or rechargeable battery to provide electrons to the system to produce and store hydrogen.

[0055] It also includes a sliding rheostat 4, which is a miniature rotary resistor that can adjust the current in the circuit without any range.

[0056] It also includes switch 2, which is used to start and stop the circuit. Switch 2 uses a brush connection, which greatly reduces the size and improves operability.

[0057] It also includes a hydrogen flow control disc 1: made of PEEK material, the surface of the hydrogen flow control disc 1 is engraved with corresponding gear indicators to facilitate the selection of hydrogen flow.

[0058] This invention includes three working modes: electrically controlled hydrogen release, electrically controlled hydrogen storage, and preservation mode, which can achieve long-term sealed storage after power failure.

[0059] The specific working principle is as follows: Electrically controlled hydrogen release mode: First, the hydrogen flow control disk 1 is moved to the ideal flow mark. Then, switch 2 is pressed to connect the circuit, apply polarization voltage and release constant current. Hydrogen is deintercalated into protons in the anode lattice. As the protons migrate to the cathode through the proton membrane 12, high-purity hydrogen is generated under the catalysis of the platinum-titanium mesh 13. During the hydrogen release process, the current is linearly proportional to the hydrogen release flow rate.

[0060] Reaction formula: XXHx→XX+xH + +xe - 2H + +2e - →H2↑ Power-off locking: After power is cut off, there is no external electric potential. At the same time, there are tiny cavities between the hydrogen storage material and the proton exchange membrane 12. The hydrogen in the lattice cannot be inserted or removed and migrated. The self-release hydrogen rate approaches 0, thus achieving long-term sealed storage.

[0061] Electro-controlled hydrogen storage mode: First, flip the battery 5 over and add ultrapure water to the through hole on the lower cover 8 so that the ultrapure water wets the proton exchange membrane 12 and the platinum-titanium mesh 13. Then, adjust the hydrogen flow control disk 1 to control the output current and realize the hydrogen storage function.

[0062] A closed micro-cavity is formed between the proton exchange membrane 12 and the hydrogen storage material 10 through a fluororubber insulating sealing ring 11, and the two do not have direct hard contact. In the working state, the saturated water vapor on the surface of the proton exchange membrane 12 and the humid atmosphere in the micro-cavity form a hydrated proton conduction medium, and hydrogen protons can diffuse across the gap through the gas phase humid environment to ensure the normal conduction of the electrochemical circuit. In the static state, the non-contact structure completely cuts off the micro-electronic conduction path at the interface, eliminates the spontaneous hydrogen evolution reaction of the galvanic cell, and realizes long-term sealing of the hydrogen storage material.

[0063] Specifically, the hydrogen storage material 10 is preferably 100-300 mesh powder and is molded by compression molding at 5-10 MPa.

[0064] Proton exchange membrane 12 pretreatment: preferably wetted with ultrapure water for 5-20 min, until there is no free water on the surface.

[0065] Casing pressure resistance: rated 0.3MPa, limit 0.6MPa.

[0066] Hydrogen release flow rate: adjustable from 0.5 to 10 μL / min.

[0067] Start-stop characteristics: Gas is generated instantaneously when power is applied, and hydrogen release stops within 1 second when power is cut off.

[0068] Example 1: use Figure 1The structure shown uses PEEK material for the upper cover 7 and the lower cover 8, which are fastened together. The gaps are sealed with anaerobic sealant to achieve permanent airtightness. The lower cover 8 has two 0.2mm diameter vents, and the cathode interface is integrated on the side of the lower cover 8. The upper cover 7 is a composite structure. The lower side of the upper cover 7 is used to fasten with the lower cover 8, and the upper side of the upper cover 7 has a terminal post, which is used to integrate the battery 5, the sliding rheostat 4, the switch 2, and the brush ring 3. The hydrogen storage material 10 is ZrNi5, and the proton exchange membrane 12 is Nafion 212. The overall pressure resistance range is 0.3-0.6MPa. ZrNi5 is selected as the hydrogen storage material 10. Under normal temperature and pressure conditions and without external bias, it does not release hydrogen gas. Pressing the self-locking push-button switch 2 generates an adjustable positive voltage of 0.1-0.4V relative to the platinum-titanium mesh 13 on the ZrNi5Hx, causing hydrogen atoms to convert into hydrogen protons. These protons then pass through the proton exchange membrane 12 and reach the cathode, where they are converted into hydrogen gas, thus achieving the effect of releasing hydrogen gas at different rates. Pressing the switch again stops the power supply, ending the hydrogen release process.

[0069] The normally closed, electrically controlled, semi-solid micro hydrogen release box designed in this invention has the functions of releasing hydrogen upon energization and locking hydrogen upon power failure. Simultaneously, the hydrogen flow rate can be precisely controlled from 0.5-10 μL / min by adjusting the voltage and current according to the application scenario. Furthermore, by adding ultrapure water to the proton exchange membrane 12 to wet it and applying a negative voltage of 0.8-1V relative to the platinum-titanium mesh 13, hydrogen filling and recycling can be achieved.

[0070] In the description of this invention, it should be understood that the terms "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this invention, and are not intended to 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 invention.

[0071] The above embodiments are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. An electrically controlled reversible miniature hydrogen release box for supplying hydrogen to a hydrogen reference electrode, characterized in that, include: A sealed housing assembly, and a power supply and a hydrogen reaction device disposed within the sealed housing assembly, the hydrogen reaction device being connected to the power supply; The power supply can switch polarity; The hydrogen reaction device includes a first unit, a second unit, and a proton membrane (12) disposed between the two. A sealed micro-gas chamber is provided between the proton membrane (12) and the first unit. The first unit includes a hydrogen storage material (10), and the sealed micro-gas cavity is disposed between the hydrogen storage material (10) and the proton membrane (12); The hydrogen reactor has a hydrogen release mode, a hydrogen storage mode, and a hydrogen preservation mode; When the hydrogen reaction device is in the hydrogen release mode, after the proton membrane (12) is wetted with ultrapure water, the first unit acts as the anode and the second unit acts as the cathode, so that the hydrogen atoms in the hydrogen storage material (10) lose electrons and become hydrogen protons, which pass through the proton membrane (12) to reach the second unit to obtain electrons and form hydrogen gas. When the hydrogen reaction device is in the hydrogen storage mode, after the proton membrane (12) is wetted with ultrapure water, the first unit acts as the cathode and the second unit acts as the anode, so that the water molecules in the second unit are converted into hydrogen protons and pass through the proton membrane (12) to reach the first unit. The hydrogen protons combine with electrons and enter the hydrogen storage material (10) to complete the hydrogen storage. When the hydrogen reaction device is in storage mode, both the first unit and the second unit are disconnected from the power supply, and the sealed micro-gas cavity blocks the hydrogen proton conduction path.

2. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 1, characterized in that, The sealed housing assembly includes an upper cover (7) and a lower cover (8), which are fixedly disposed. The power supply is disposed inside the upper cover (7), and the hydrogen reaction device is disposed inside the lower cover (8).

3. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 2, characterized in that, The first unit also includes a dense graphite current collector (9) fixed to one end of the hydrogen storage material (10), and the dense graphite current collector (9) is fixed to one end of the upper cover (7); The dense graphite current collector (9) is connected to the power source.

4. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 2, characterized in that, The second unit includes a platinum-plated titanium mesh (13), which is in contact with the side of the proton membrane (12) away from the micro-cavity spacer. It also includes a porous graphite current collector (14), which is fixed inside the lower cover (8) and in contact with the platinum-plated titanium mesh (13); The porous graphite current collector (14) is connected to the power source; When the hydrogen reaction device is in the hydrogen release mode, the platinum-plated titanium mesh (13) acts as a cathode, allowing hydrogen protons to gain electrons on its surface to generate hydrogen gas. When the hydrogen reactor is in the hydrogen storage mode, the platinum-plated titanium mesh (13) acts as the anode, causing ultrapure water to lose electrons on its surface to generate oxygen and hydrogen protons. The lower cover (8) is provided with multiple through holes, which are used for gas discharge or for ultrapure water replenishment.

5. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 1, characterized in that, The power source includes a battery (5), the polarity of which is switched by flipping the battery (5).

6. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 2, characterized in that, It also includes an adjustment device connected to the power supply, which is used to adjust the current of the power supply.

7. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 6, characterized in that, The adjustment device includes a sliding rheostat (4), and the first unit and the second unit are connected to the power supply through the sliding rheostat (4); The movable end of the sliding rheostat (4) is connected to a hydrogen flow control disk (1), the hydrogen flow control disk (1) is rotatably engaged with the upper cover (7), and the fixed end of the sliding rheostat (4) is fixed inside the upper cover (7).

8. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 7, characterized in that, A switch (2) is provided between the sliding rheostat (4) and the power supply.

9. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 1, characterized in that, A fluororubber insulating sealing ring (11) is provided between the proton exchange membrane (12) and the hydrogen storage material (10), and the fluororubber insulating sealing ring (11), the proton exchange membrane (12) and the hydrogen storage material (10) together form the sealed micro-gas cavity.

10. The electrically controlled reversible micro hydrogen release box for hydrogen supply to a hydrogen reference electrode according to claim 1, characterized in that, The hydrogen storage material (10) is formed by molding 100-300 mesh hydrogen storage material powder, with a molding pressure of 5-10 MPa.

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