Solid electrolyte hydrogen concentration sensor

Abstract

The utility model relates to a solid electrolyte hydrogen concentration sensor which comprises a substrate, a hydrogen sensing film and a heating device, a first surface of the substrate is provided with a gas circulation groove, one end of the gas circulation groove is a gas inlet end, and the gas circulation groove forms a through hole in the first surface; the hydrogen sensing film comprises an electrolyte film arranged on the first surface, a cathode film arranged on the surface of the side, facing the substrate, of the electrolyte film and an anode film arranged on the surface of the side, back to the substrate, of the electrolyte film, the electrolyte film covers the penetrating opening, the cathode film is located in the gas circulation groove, and the heating device is arranged on the substrate. During detection, the cathode film is in contact with oxygen in air to form oxygen anions, the anode film is in contact with hydrogen to form hydrogen ions, the hydrogen ions penetrate through the electrolyte film and react with the oxygen anions of the cathode film, a current signal is generated, the current intensity and the hydrogen concentration are in a linear relation, and the hydrogen concentration can be obtained according to the current intensity. The sensor can stably work in a high-temperature and high-humidity weak acid environment, so that tail emission application is met.

Description

TECHNICAL FIELD

[0001] The utility model relates to new energy equipment technical field, especially a kind of solid electrolyte hydrogen concentration sensor. BACKGROUND

[0002] New energy fuel cell vehicle is gradually developed, fuel cell vehicle only consumes hydrogen and oxygen, generates electricity while generating water, and this "zero emission" can be said to be the ultimate form of new energy vehicle. But in view of the wide explosion range of hydrogen, it is easy to diffuse, it is difficult to store and other characteristics, the leakage detection of hydrogen in hydrogen fuel cell vehicle is an important early warning mechanism to ensure the safety of vehicle personnel. Therefore, high-stability and high-reliability solid electrolyte hydrogen concentration sensor plays a significant role in the safety of hydrogen fuel cell vehicle.

[0003] At present, in fuel cell system, hydrogen and oxygen react on both sides of proton exchange membrane inside the stack, and water is generated on the air side. The unreacted hydrogen and generated water are discharged through the exhaust pipe. The hydrogen utilization rate of fuel cell stack is a key indicator affecting the performance of fuel cell. If there is a high concentration of hydrogen in the tail exhaust, it not only leads to low efficiency of fuel cell system, but also may cause hydrogen enrichment and explosion, causing safety accidents. Therefore, hydrogen concentration detection of fuel cell system tail exhaust is very critical and necessary. Since the hydrogen discharged by the fuel cell system is in a high-temperature, high-humidity and weakly acidic environment, and contains a certain amount of hydrogen, the working environment is very harsh. Therefore, how to provide a solid electrolyte hydrogen concentration sensor that meets the tail exhaust application is an important technical problem to be solved by those skilled in the art. UTILITY MODEL CONTENTS

[0004] The utility model aims at providing a kind of solid electrolyte hydrogen concentration sensor, to make it can meet tail exhaust application.

[0005] To achieve the above object, the utility model provides the following technical scheme:

[0006] A kind of solid electrolyte hydrogen concentration sensor, comprising:

[0007] The first surface of the substrate is provided with a gas flow channel, one end of the gas flow channel in the extension direction is an air inlet end, and the gas flow channel forms a through hole in the first surface;

[0008] The hydrogen sensing film includes an electrolyte film, a cathode film and an anode film. The electrolyte film is arranged on the first surface, and covers the through hole. The cathode film is arranged on the side surface of the electrolyte film facing the substrate, and is located in the gas flow channel. The anode film is arranged on the side surface of the electrolyte film away from the substrate.

[0009] a heating device disposed on the substrate.

[0010] In an embodiment of the present application, one end of the gas flow channel away from the gas inlet end is a closed end.

[0011] In an embodiment of the present application, the projection of the anode film on the plane of the first surface at least partially overlaps the projection of the cathode film on the plane of the first surface, and the projection of the anode film on the plane of the first surface at least partially overlaps the projection of the gas flow channel on the plane of the first surface.

[0012] In an embodiment of the present application, the projection of the anode film on the plane of the first surface overlaps the projection of the cathode film on the plane of the first surface, and both are located within the projection of the gas flow channel on the plane of the first surface.

[0013] In an embodiment of the present application, the hydrogen sensing film further comprises a cathode film overlap block, the electrolyte film is provided with a conductive via, and the cathode film overlap block is disposed on the side surface of the electrolyte film away from the substrate, and the cathode film overlap block is electrically connected to the cathode film through the conductive via.

[0014] In an embodiment of the present application, the substrate comprises a second surface disposed opposite to the first surface, and the heating device is disposed on the second surface.

[0015] In an embodiment of the present application, the first surface and / or the second surface is provided with a silicon dioxide film.

[0016] In an embodiment of the present application, the projection of the heating device on the plane of the first surface at least partially overlaps the projection of the hydrogen sensing film on the plane of the first surface.

[0017] In an embodiment of the present application, the heating device is a conductive electrode wire, and the conductive electrode wire is coiled and disposed on the second surface.

[0018] In an embodiment of the present application, further comprising a packaging shell, the substrate, the hydrogen sensing film, and the heating device are disposed in the packaging shell, the packaging shell is connected to the exhaust pipe of the hydrogen fuel system through a detachable connection structure, the anode film is located in the exhaust pipe of the hydrogen fuel system, and the gas inlet end of the gas flow channel is located outside the exhaust pipe of the hydrogen fuel system.

[0019] From the above technical scheme can be seen, the utility model discloses a kind of solid electrolyte hydrogen concentration sensors, the solid electrolyte hydrogen concentration sensor includes base, hydrogen sensing film and heating device, wherein, the first surface of base is provided with gas flow groove, one end in the extension direction of gas flow groove is gas inlet end, gas flow groove forms through hole in first surface, hydrogen sensing film includes electrolyte film, cathode film and anode film, electrolyte film is arranged on first surface, and electrolyte film covers through hole, cathode film is arranged on the side surface of electrolyte film towards base, and cathode film is located in gas flow groove, anode film is arranged on the side surface of electrolyte film away from base, heating device is arranged on base.

[0020] When applied, the above solid electrolyte hydrogen concentration sensor is connected to the exhaust pipe of hydrogen fuel system, to ensure that the anode film is located in the exhaust pipe of hydrogen fuel system, the gas inlet end of gas flow groove is located outside the exhaust pipe of hydrogen fuel system, so that the anode film contacts the exhaust gas to be detected, the cathode film contacts air, the heat generated by the heating device is transmitted to the hydrogen sensing film through the base, so that the hydrogen sensing film is kept at a working temperature, at which the electrolyte film in the hydrogen sensing film becomes a good conductor of hydrogen, the anode film contacts hydrogen in the gas to be detected and forms hydrogen ions, the cathode film contacts oxygen in air and forms oxygen negative ions, hydrogen ions on the anode film penetrate the electrolyte film, react with oxygen negative ions of the cathode film to generate water vapor and generate an electric current signal, and the hydrogen concentration in the exhaust pipe and the electric current intensity output by the hydrogen sensing film show a linear relationship, so that the hydrogen concentration in the exhaust pipe can be obtained by measuring the electric current intensity, and the structure design of the above solid electrolyte hydrogen concentration sensor enables it to work stably in a high-temperature, high-humidity and weak-acid environment, thereby meeting the requirements of tail exhaust applications. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0022] Figure 1 A transverse cross-sectional view of the solid electrolyte hydrogen concentration sensor provided by the embodiments of the present application is shown in the figure.

[0023] Figure 2 A longitudinal cross-sectional view of the solid electrolyte hydrogen concentration sensor provided by the embodiments of the present application is shown in the figure.

[0024] Figure 3 A top view of the solid electrolyte hydrogen concentration sensor provided by the embodiments of the present application is shown in the figure.

[0025] Figure 4 The utility model provides a solid electrolyte hydrogen concentration sensor's plan view for an embodiment of the utility model,

[0026] Figure 5 The utility model provides a solid electrolyte hydrogen concentration sensor's plan view for another embodiment of the utility model.

[0027] In the drawing,

[0028] 10 is a substrate; 101 is a first surface; 102 is a second surface; 103 is a gas flow groove;

[0029] 20 is a hydrogen sensing film; 201 is an electrolyte film; 202 is a cathode film; 203 is an anode film; 2031 is a second connecting end;

[0030] 30 is a conductive electrode wire;

[0031] 40 is a cathode film lap block; 401 is a first connecting end. DETAILED DESCRIPTION

[0032] The utility model discloses a solid electrolyte hydrogen concentration sensor, the structural design of the solid electrolyte hydrogen concentration sensor makes it.

[0033] The technical solutions in the embodiments of the utility model will be clearly and completely described with reference to the drawings in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model and not all the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the utility model.

[0034] Please refer to Figure 1 And Figure 2 , Figure 1 The utility model provides a solid electrolyte hydrogen concentration sensor's cross section schematic view for the embodiment of the utility model, Figure 2 The utility model provides a solid electrolyte hydrogen concentration sensor's longitudinal section schematic view for the embodiment of the utility model.

[0035] The utility model discloses a solid electrolyte hydrogen concentration sensor, the solid electrolyte hydrogen concentration sensor includes substrate 10, hydrogen sensing film 20 and heating device.

[0036] In order for the hydrogen sensing film 20 to work normally, the substrate 10 needs to have good thermal conductivity to timely transmit the heat generated by the heating device to the hydrogen sensing film 20, and thus the substrate 10 is made of a material that is resistant to high temperature and has good thermal conductivity, such as single crystal silicon or polycrystalline silicon. Of course, the material for making the substrate 10 is not limited to these two, and the size of the substrate 10 can be designed by those skilled in the art as needed. In an embodiment of the present application, the length of the substrate 10 is 30-70 mm, the width is 3-7 mm, and the thickness is 2-5 mm. The first surface 101 of the substrate 10 is formed with a gas flow groove 103 by a MEMS process or a laser process. One end of the gas flow groove 103 in the extension direction is an air inlet end for air to enter. The gas flow groove 103 forms a through hole in the first surface 101. Further, in a specific embodiment of the present application, the extension direction of the gas flow groove 103 is the length direction of the substrate 10. The depth of the gas flow groove 103 is less than the thickness of the substrate 10. The length of the gas flow groove 103 is less than the length of the substrate 10. The width of the gas flow groove 103 is less than the width of the substrate 10. The length of the gas flow groove 103 is 28-68 mm, the width is 0.1-0.5 mm, and the depth is 0.1-0.5 mm.

[0037] The hydrogen sensing film 20 includes an electrolyte film 201, a cathode film 202, and an anode film 203. The electrolyte film 201 is a high-temperature proton ceramic conductor, mainly composed of BaCeO3, BaZrO3, BaTbO3, SrCeO3, SrZrO3, Ba3Ca 1.18 Nb 1.82 O 9-δ or a mixture of two or more components. The electrolyte film 201 becomes a good conductor of hydrogen when it reaches the working temperature. The electrolyte film 201 is arranged on the first surface 101 and covers the through hole. The anode film 203 and the cathode film 202 are composed of platinum-palladium nanoparticles. The cathode film 202 is arranged on the side surface of the electrolyte film 201 facing the substrate 10 and is located in the gas flow groove 103. The anode film 203 is arranged on the side surface of the electrolyte film 201 away from the substrate 10. The cathode film 202 and the anode film 203 are electrically connected to the controller of the hydrogen fuel system through signal electrodes.

[0038] The heating device is arranged on the substrate 10 and includes but is not limited to a heating film and a conductive electrode wire 30. The power supply for the heating device can be a battery provided by the solid-state electrolyte hydrogen concentration sensor itself or an external power supply, such as a hydrogen fuel system.

[0039] Compared with the prior art, the solid-state electrolyte hydrogen concentration sensor provided by the embodiment of the utility model is connected to the exhaust pipe of the hydrogen fuel system, the anode film 203 is located in the exhaust pipe of the hydrogen fuel system, the gas inlet end of the gas flow groove 103 is located outside the exhaust pipe of the hydrogen fuel system, the anode film 203 contacts with the exhaust gas to be detected, the cathode film 202 contacts with the air, the heat generated by the heating device is transmitted to the hydrogen sensing film 20 through the substrate 10, the hydrogen sensing film 20 is kept at the working temperature, at the working temperature, the electrolyte film 201 in the hydrogen sensing film 20 becomes a good conductor of hydrogen, the anode film 203 contacts with the hydrogen in the gas to be detected and forms hydrogen ions, the cathode film 202 contacts with the oxygen in the air and forms oxygen negative ions, the hydrogen ions on the anode film 203 penetrate the electrolyte film 201, react with the oxygen negative ions of the cathode film 202 to generate water vapor, and generate an electric current signal, the hydrogen concentration in the exhaust pipe and the electric current intensity output by the hydrogen sensing film 20 present a linear relationship, the hydrogen concentration in the exhaust pipe can be obtained by measuring the size of the output electric current intensity, and the structure design of the solid-state electrolyte hydrogen concentration sensor enables it to work stably in a high-temperature, high-humidity and weak-acid environment, thereby meeting the requirements of tail exhaust applications.

[0040] In order to increase the contact time of air and the cathode film 202, in a preferred embodiment of the present application, as shown in Figure 2 The end of the gas flow groove 103 away from the gas inlet end in the extension direction is a closed end, that is, the gas flow groove 103 is only communicated with the outside at the gas inlet end and is closed in other directions.

[0041] In order to facilitate the reaction of hydrogen ions of the anode film 203 and oxygen negative ions on the cathode film 202, in an embodiment of the present application, the projection of the anode film 203 on the plane of the first surface 101 at least partially overlaps the projection of the cathode film 202 on the plane of the first surface 101, and the projection of the anode film 203 on the plane of the first surface 101 at least partially overlaps the projection of the gas flow groove 103 on the plane of the first surface 101.

[0042] Further optimization of the above technical solution, the projection of the anode film 203 on the plane of the first surface 101 overlaps the projection of the cathode film 202 on the plane of the first surface 101, and both are located in the projection of the gas flow groove 103 on the plane of the first surface 101, that is, the length and width of the anode film 203 and the length and width of the cathode film 202 are consistent respectively, and both are located at the center position of the gas flow groove 103, and the width of the anode film 203 and the width of the cathode film 202 are both less than the width of the gas flow groove 103.

[0043] In order to facilitate the signal of the cathode film 202 to be led out, in an embodiment of the present application, please refer toFigure 2 and Figure 3 , Figure 2 A longitudinal section view of a solid-state electrolyte hydrogen concentration sensor is provided in the embodiments of the present application, Figure 3 A plan view of a solid-state electrolyte hydrogen concentration sensor is provided in the embodiments of the present application, the hydrogen sensing film 20 further comprises a cathode film lap block 40, the electrolyte film 201 is provided with a conductive via, the cathode film lap block 40 is arranged on the side surface of the electrolyte film 201 away from the substrate 10, and the cathode film lap block 40 is electrically connected with the cathode film 202 through the conductive via, so that the connection end of the cathode film 202 and the anode film 203 and the signal electrode can be arranged on the side surface of the solid-state electrolyte hydrogen concentration sensor, facilitating the connection of the signal electrode.

[0044] Further, as shown in Figure 3 , the cathode film lap block 40 is provided with a first connection end 401 extending to the first side of the hydrogen sensing film 20 at one end of the side of the electrolyte film 201 away from the substrate 10, and the anode film 203 is provided with a second connection end 2031 extending to the second side of the hydrogen sensing film 20 at one end close to the cathode film lap block 40, and the first connection end 401 and the second connection end 2031 are respectively used for connecting with the signal electrode, so as to increase the distance between the first connection end 401 and the second connection end 2031.

[0045] As shown in Figure 1 and Figure 2 , in an embodiment of the present application, the substrate 10 comprises a second surface 102 arranged opposite to the first surface 101, and the heating device is arranged on the second surface 102 to ensure uniform heating of the hydrogen sensing film 20, of course, the heating device can also be arranged on other surfaces of the substrate 10, or heating devices are arranged on other surfaces of the substrate 10 except the first surface 101, in the embodiment of the present application, the heating device can completely cover the second surface 102, as shown in Figure 4 , or only cover part of the second surface 102, as shown in Figure 5 , the coverage area of the heating device can be designed according to the working area size of the hydrogen sensing film 20, different coverage areas are designed according to different sizes, which can more greatly ensure the working temperature of the hydrogen sensing film 20 and can reach the minimum energy consumption, the heating device completely covers the second surface 102 of the substrate 10, so that the second surface 102 of the substrate 10 can be heated by the heating device, which can ensure the comprehensiveness of heating, but due to the outward diffusion of heat, the heat of the heating device relative to the middle region will be relatively stable, so the functional device is preferably arranged in the middle region of the second surface 102 of the substrate 10 to ensure the stability of its work, and also saves energy, and utilizes the temperature in the middle to diffuse to both sides to increase the heating balance of the hydrogen sensing film 20.

[0046] In an embodiment of the present application, the heating device is a conductive electrode wire 30, which is coiled on the second surface 102. The coiling manner of the conductive electrode wire 30 includes spiral coiling, serpentine coiling, zigzag coiling, etc. Please refer to Figure 4 and Figure 5 As shown, the conductive electrode wire 30 with different shapes is given, Figure 4 The conductive electrode wire 30 given in the above embodiment is coiled in a rectangular wave shape, from Figure 4 It can be seen from the above embodiment that, in this embodiment, the conductive electrode wire 30 covers the second surface 102 of the substrate 10; while Figure 5 Another arrangement of the conductive electrode wire 30 is given, compared with Figure 4 , Figure 5 In the embodiment shown, the coiling manner of the conductive electrode wire 30 is the same, but the coverage is only about half of the second surface 102 of the substrate 10, and the heating device only partially covers the second surface 102 of the substrate 10.

[0047] As a preference, in an embodiment of the present application, the projection of the heating device on the plane of the first surface 101 at least partially overlaps the projection of the hydrogen sensing film 20 on the plane of the first surface 101, so as to ensure that the hydrogen sensing film 20 can be effectively heated.

[0048] The heating device further includes a temperature detection device, which is arranged on the substrate 10 and is used to detect the temperature of the substrate 10. The temperature detection device can be electrically connected to the controller of the hydrogen fuel system, and the controller of the hydrogen fuel system controls the on-off of the circuit of the heating device according to the detection value of the temperature detection device, so as to realize the control of the working temperature of the solid electrolyte hydrogen concentration sensor.

[0049] Further optimization of the above technical solution, in an embodiment of the present application, the first surface 101 and / or the second surface 102 is provided with a silicon dioxide film, which can protect the surface of the substrate 10 and has an insulating isolation effect.

[0050] As preferred, the solid electrolyte hydrogen concentration sensor further comprises a packaging shell, the substrate 10, the hydrogen sensing film 20 and the heating device are arranged in the packaging shell, the packaging shell is connected with the exhaust pipe of the hydrogen fuel system through a detachable connecting structure, the anode film 203 is located in the exhaust pipe of the hydrogen fuel system, the gas flow groove 103 is located outside the exhaust pipe of the hydrogen fuel system, the first electrically connecting structure for electrically connecting the heating device with the heating power supply and the second electrically connecting structure for electrically connecting the cathode film 202 and the anode film 203 with the signal electrode are arranged on the packaging shell, that is, the packaging shell not only plays the role of placing, fixing and protecting the substrate 10, the hydrogen sensing film 20 and the heating device, but also enhances the heat conduction performance, and is also a bridge for connecting the internal structure of the solid electrolyte hydrogen concentration sensor with the external circuit.

[0051] It should be noted that each of the embodiments in the specification is described in a progressive manner, and each embodiment focuses on the difference from other embodiments, and the same or similar parts between the embodiments can be referred to each other.

[0052] The principle and implementation mode of the present application are described by using specific examples, and the above embodiment is only used to help understand the core idea of the present application. It should be pointed out that for ordinary skilled in the art, without departing from the principle of the present application, the present application can be improved and modified, and these improvements and modifications also fall within the protection scope of the present application.

Claims

1. A solid state electrolyte hydrogen concentration sensor, characterized by, include: A substrate, wherein a gas circulation groove is provided on a first surface of the substrate, one end of the gas circulation groove in an extending direction is a gas inlet end, and the gas circulation groove forms a through opening on the first surface; A hydrogen sensing membrane, the hydrogen sensing membrane comprising an electrolyte membrane, a cathode membrane, and an anode membrane, the electrolyte membrane being disposed on the first surface and covering the through-hole, the cathode membrane being disposed on a surface of the electrolyte membrane facing the substrate and being located within the gas flow groove, and the anode membrane being disposed on a surface of the electrolyte membrane facing away from the substrate; A heating device is provided on the substrate.

2. The solid-state electrolyte hydrogen concentration sensor of claim 1, wherein, The end of the gas circulation groove that is away from the gas inlet end in the extending direction is a closed end.

3. The solid state electrolyte hydrogen concentration sensor of claim 1, wherein, The projection of the anode film on the plane where the first surface is located at least partially overlaps with the projection of the cathode film on the plane where the first surface is located, and the projection of the anode film on the plane where the first surface is located at least partially overlaps with the projection of the gas flow groove on the plane where the first surface is located.

4. The solid state electrolyte hydrogen concentration sensor of claim 3, wherein, The projection of the anode film on the plane where the first surface is located overlaps with the projection of the cathode film on the plane where the first surface is located, and both are located within the projection of the gas flow groove on the plane where the first surface is located.

5. The solid-state electrolyte hydrogen concentration sensor according to any one of claims 1 to 4, characterized by, The hydrogen sensor membrane also includes a cathode membrane overlap block. The electrolyte membrane is provided with a conductive via. The cathode membrane overlap block is arranged on the side surface of the electrolyte membrane facing away from the substrate. The cathode membrane overlap block is electrically connected to the cathode membrane through the conductive via.

6. The solid-state electrolyte hydrogen concentration sensor according to any one of claims 1 to 4, characterized by, The substrate includes a second surface disposed opposite to the first surface, and the heating device is disposed on the second surface.

7. The solid state electrolyte hydrogen concentration sensor of claim 6, wherein, The first surface and / or the second surface is provided with a silicon dioxide film.

8. The solid state electrolyte hydrogen concentration sensor of claim 6, wherein, The projection of the heating device on the plane where the first surface is located at least partially overlaps with the projection of the hydrogen sensing film on the plane where the first surface is located.

9. The solid state electrolyte hydrogen concentration sensor of claim 6, wherein, The heating device is a conductive electrode wire, and the conductive electrode wire is coiled and arranged on the second surface.

10. The solid-state electrolyte hydrogen concentration sensor according to any one of claims 1 to 4 and 7 to 9, characterized by, It also includes a packaging shell, the substrate, the hydrogen sensor membrane and the heating device are arranged in the packaging shell, the packaging shell is connected to the exhaust pipe of the hydrogen fuel system through a detachable connection structure, and the anode membrane is located in the exhaust pipe of the hydrogen fuel system, and the air inlet end of the gas circulation groove is located outside the exhaust pipe of the hydrogen fuel system.

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