CN108254420B - Hydrogen sensor for rapidly detecting low-concentration hydrogen - Google Patents
Hydrogen sensor for rapidly detecting low-concentration hydrogen Download PDFInfo
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- CN108254420B CN108254420B CN201611237762.9A CN201611237762A CN108254420B CN 108254420 B CN108254420 B CN 108254420B CN 201611237762 A CN201611237762 A CN 201611237762A CN 108254420 B CN108254420 B CN 108254420B
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
Abstract
The invention relates to a hydrogen sensor for rapidly detecting low-concentration hydrogen, which comprises a shell, wherein a gas detection unit is arranged in the shell, the gas detection unit comprises an electrolyte layer, a working electrode, a counter electrode and a reference electrode which are integrated with the electrolyte layer, a gas diffusion membrane is arranged at one side of the shell facing the working electrode, a working electrode reaction air chamber for the reaction of the hydrogen on the working electrode is formed between the gas diffusion membrane and the working electrode in a sealing way through a sealing piece, the gas diffusion membrane is of a non-porous structure, and the electrolyte layer is a solid electrolyte layer or a semi-solid electrolyte layer. The hydrogen sensor for rapidly detecting low-concentration hydrogen has very rapid response, can cope with safety monitoring of places where hydrogen is accumulated instantaneously, can rapidly and accurately detect low-concentration hydrogen in a severe environment, and is widely applicable to hydrogen monitoring in the fields of vehicles, power plants, nuclear power and the like.
Description
Technical Field
The invention relates to the technical field of hydrogen sensors, in particular to a hydrogen sensor for rapidly detecting low-concentration hydrogen.
Background
The current hydrogen detection methods include the following:
(1) A semiconductor sensor: the semiconductor material is detected by the change of the resistance before and after contacting hydrogen, and the method has the advantages of high response speed; the defect is that the hydrogen detection with the concentration higher than the percentage can be carried out, and the semiconductor element is easy to generate faults such as fusing and the like when working at high temperature for a long time; meanwhile, the shock resistance is poor, and the phenomenon of organosilicon poisoning can exist;
(2) Catalytic combustion type sensor: the detecting element is heated to a high temperature of hundreds of degrees, so that the hydrogen is subjected to combustion reaction on the detecting element, and the current generated by the detecting element is detected, and has the advantages and disadvantages basically the same as those of a semiconductor sensor;
(3) Electrochemical sensor: the hydrogen is detected by a fixed potential electrolytic method by using the corresponding products of the British urban technical company as representatives, the PPM-level hydrogen content can be detected, and the rapid diagnosis under emergency conditions cannot be provided, and the method is not suitable for extreme environments such as high temperature, high humidity, low temperature, low humidity and the like, and has short service life, especially limited service life under severe environments;
(4) A fuel cell type sensor: the detection of gases is typically carried out by micro fuel cells, represented by the GE company and the DART company in the united kingdom, the former produces sensors having long life, which can be suitable for extreme environments and other outstanding advantages, but which, while acquiring the above advantages, sacrifice the detection speed of the sensor and are therefore unsuitable for places where high concentrations of hydrogen may accumulate instantaneously; the sensor produced by the latter has a high response speed, but cannot be suitable for severe environments;
(5) Thin film capacitive French sensor: the sensor is typically represented by a corresponding product of H2Scan company, has the outstanding advantages of quick response, suitability for severe environments, long trial life and the like, but the sensor cannot detect low-concentration hydrogen.
Disclosure of Invention
The invention aims to provide a hydrogen sensor for rapidly detecting low-concentration hydrogen, which solves the problem that the hydrogen sensor in the prior art cannot rapidly detect low-concentration hydrogen under severe conditions.
The technical scheme adopted for solving the technical problems is as follows: the utility model provides a hydrogen sensor for short-term test low concentration hydrogen, includes the casing install the gas detection unit in the casing, the gas detection unit include the electrolyte layer and with the working electrode, counter electrode and the reference electrode that the electrolyte layer combines into an organic whole, the casing is interior towards one side of working electrode installs the gas diffusion membrane, the gas diffusion membrane with form through the sealing member is sealed between the working electrode and be used for the hydrogen to take place the working electrode reaction air chamber of reaction on the working electrode, the gas diffusion membrane is the gas diffusion membrane of non-porous structure, the electrolyte layer is solid electrolyte layer or semi-solid electrolyte layer.
In the hydrogen sensor of the present invention, the distance between the working electrode and the opposite sides of the gas diffusion membrane is 0.01mm to 100mm.
In the hydrogen sensor of the present invention, the thickness of the gas diffusion film is 0.001mm to 0.1mm.
In the hydrogen sensor of the present invention, the gas diffusion membrane is a gas diffusion membrane made of any one or a mixture of several of polytetrafluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-perfluoropropyl vinyl ether copolymer, polyethylene-tetrafluoroethylene copolymer, polyimide, silicone rubber, and fluorinated silicone rubber.
In the hydrogen sensor, the shell comprises a main body with an opening and a cover body covered at the opening of the main body, a sealing ring is arranged on the side wall of the cover body, and a notch matched with the sealing ring is formed on the inner wall of the opening of the shell.
In the hydrogen sensor of the present invention, the working electrode is located on one side of the electrolyte layer, the counter electrode and the reference electrode are located on the other side of the electrolyte layer, and the counter electrode and the reference electrode are juxtaposed on the other side of the electrolyte layer.
In the hydrogen sensor of the present invention, an oxygen storage space for storing oxygen is formed below the counter electrode, and the volume of the oxygen storage space is 0.1-100ml.
In the hydrogen sensor of the present invention, the initial humidity in the housing is 50% RH to 90% RH.
In the hydrogen sensor of the present invention, the electrolyte layer is a solid electrolyte layer prepared from a phenol resin sulfonic acid type film, a polystyrene sulfonic acid type film, a polytrichlorostyrene sulfonic acid type film or a perfluorosulfonic acid type film.
In the hydrogen sensor of the invention, the electrolyte layer is a semi-solid electrolyte layer, the semi-solid electrolyte layer comprises a porous substrate, and semi-fluidity capillary colloid for mass transfer is filled in micropores of the porous substrate; the capillary colloid comprises nano porous particles and acidic electrolyte adsorbed on the nano porous particles, and the volume ratio of the nano porous particles to the acidic electrolyte is 0.1-1.2.
The hydrogen sensor for rapidly detecting low-concentration hydrogen has the following beneficial effects: the hydrogen sensor for rapidly detecting low-concentration hydrogen has very rapid response, can cope with safety monitoring of places where hydrogen is accumulated instantaneously, can rapidly and accurately detect low-concentration hydrogen in a severe environment, and is widely applicable to hydrogen monitoring in the fields of vehicles, power plants, nuclear power and the like.
Drawings
FIG. 1 is a schematic diagram of a hydrogen sensor for rapidly detecting low concentration hydrogen according to the present invention;
FIG. 2 is a graph showing the response time of a hydrogen sensor for rapidly detecting low concentration hydrogen according to the present invention, compared with a hydrogen sensor of the prior art;
FIG. 3 is a graph comparing the performance of a hydrogen sensor for rapid detection of low concentration hydrogen of the present invention with a hydrogen sensor of the prior art under extreme conditions.
Detailed Description
The hydrogen sensor for rapidly detecting low concentration hydrogen according to the present invention will be further described with reference to the accompanying drawings and examples:
in the description of the present invention, it should be understood that terms such as "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate an orientation or a positional relationship based on that shown in the drawings, are merely for convenience of description and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
As shown in fig. 1, the hydrogen sensor for rapidly detecting low concentration hydrogen gas includes a housing 1, the housing 1 includes a main body 11 having an opening and a cover body 12 covering the opening of the main body 11, a seal ring 13 is provided on a side wall of the cover body 12, a recess 14 matching the seal ring 13 is formed on an inner wall of the opening of the housing 1, and the seal ring 13 is a seal ring made of fluororubber or silicone rubber. When the hydrogen sensor needs to be applied to places such as power plants and nuclear power which have requirements on shielding performance of the hydrogen sensor, a shell 1 with shielding performance such as copper, aluminum, stainless steel and the like can be adopted; the housing 1 made of PP, ABS, PC, POM and the like can be used for reducing the cost of the whole hydrogen sensor when the hydrogen sensor needs to be applied to general industrial places, vehicles and handheld instruments.
A gas detection unit 2 is installed in the housing 1, the gas detection unit 2 includes an electrolyte layer 21, and a working electrode 22, a counter electrode 23 and a reference electrode 24 integrated with the electrolyte layer 21, wherein the working electrode 22 is located at one side of the electrolyte layer 21, the counter electrode 23 and the reference electrode 24 are located at the other side of the electrolyte layer 21, and the counter electrode 23 and the reference electrode 24 are juxtaposed at the other side of the electrolyte layer 21. The outside of the end of the shell 1 far away from the opening is provided with a first contact pin 15, a second contact pin 16 and a third contact pin 17 which are used for being in butt joint with the PCB, a working electrode 22 is electrically connected with the first contact pin 15 through a working electrode lead 25, a counter electrode 23 is electrically connected with the second contact pin 16 through a counter electrode lead 26, and a reference electrode 24 is electrically connected with the third contact pin 17 through a reference electrode lead 27. The whole hydrogen sensor is fixed on the PCB board through a first contact pin 15, a second contact pin 16 and a third contact pin 17. The working electrode 22 is a place where the gas to be measured electrochemically reacts, the counter electrode 23 is a place where oxygen in the environment electrochemically reacts, the reference electrode 24 plays a role of stabilizing a potential zero point, the electrolyte layer 21 plays a role of transferring protons, and the working electrode 22, the counter electrode 23 and the reference electrode 24 must be respectively in full contact with the electrolyte layer 21 to maintain the smoothness and the reactivity of mass transfer of the system. Two passages are formed in the gas detection unit, including a reaction passage and an output passage, wherein the reaction passage consists of a working electrode 22 and a counter electrode 23, and the gas to be detected (namely hydrogen) which is chemically reacted on the working electrode 22 and oxygen which is chemically reacted on the counter electrode 23 form a complete chemical reaction together, so that the reaction can continue; the output path is composed of the working electrode 22 and the reference electrode 24, and because phenomena such as drift and polarization of the counter electrode 23 occur in the long-term reaction process, if the potential difference of the output working electrode 22 relative to the counter electrode 23 causes the drift of the whole hydrogen sensor, the reference electrode 24 is introduced, the potential of the reference electrode 24 is stabilized at a fixed value, and usually the potential is set at the excitation potential when the gas to be detected chemically reacts on the working electrode 22, so that the detection capability of the working electrode 22 can be improved to the greatest extent. During the duration of the chemical reaction, a potential difference of the working electrode 22 with respect to the reference electrode 24 is output, so that the influence of the polarization of the counter electrode 23 on the entire hydrogen sensor can be avoided.
A gas diffusion membrane 3 is mounted in the case 1 on the side facing the working electrode 22, specifically, the gas diffusion membrane 3 is mounted on the side facing the working electrode 22 of the cover 12 of the case 1. The working electrode reaction chamber 5 for the reaction of hydrogen gas on the working electrode 22 is formed between the gas diffusion membrane 3 and the working electrode 22 by sealing by a sealing member 4, and the sealing member 4 is preferably a sealing gasket, and the thickness of the sealing gasket is preferably 0.01-10mm. In other embodiments, the sealing oil may be used, and the sealing gasket may be made of fluororubber material or silicone rubber material, preferably fluororubber material. The working electrode 22 is arranged close to the gas diffusion membrane 3, and the distance between the two opposite sides of the working electrode 22 and the gas diffusion membrane 3 is 0.01mm-100mm; preferably, the distance between the opposite sides of the working electrode 22 from the gas diffusion membrane 3 is 0.1mm to 50mm. The gas diffusion membrane 3 is a gas diffusion membrane with a non-porous structure, and the thickness of the gas diffusion membrane 3 is 0.001mm-0.1mm; preferably, the thickness of the gas diffusion membrane 3 is 0.01mm to 0.05mm. The gas diffusion membrane 3 is a gas diffusion membrane made of a mixture of one or more of polytetrafluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-perfluoropropyl vinyl ether copolymer, polyethylene-tetrafluoroethylene copolymer, polyimide, silicone rubber, and fluorinated silicone rubber.
The response speed of the sensor indicates the ability of the sensor to reach equilibrium after contacting the gas to be measured. For a sensor, the equilibrium of its output is not due to the chemical reaction stopping, but rather to the fact that the gas to be measured enters the sensor from the external environment at the same rate as it is consumed at the working electrode. The diffusion film on the conventional electrochemical hydrogen sensor usually adopts a porous film with hydrophobic property, the film is porous, and the counter electrode, the reference electrode and the working electrode of the gas detection unit in the conventional electrochemical hydrogen sensor are sequentially arranged below the porous diffusion film from top to bottom, so that the distance between the working electrode and the diffusion film is larger, and further, the diffusion film failure caused by sticking on the diffusion film when electrolyte oozes out is prevented. The hydrophobic property of the diffusion film can ensure that the sensor is not influenced by extreme conditions such as adhesion of external water drops; the porosity on the diffusion film can ensure that as many gas molecules as possible enter the sensor smoothly, thereby improving the detection accuracy of the sensor; however, the limited reactivity of the gas detection unit, due to the presence of numerous gas molecules that can enter the sensor, can cause chemical reactions of numerous molecules in the gas detection unit, which can undoubtedly extend the response time of the sensor due to the large distance between the diffusion membrane and the working electrode. In the invention, the nonporous gas diffusion membrane 3 is adopted, and the gas molecules which want to pass through the layer of gas diffusion membrane 3 are realized through the dissolution-desorption process, namely, the gas molecules are firstly dissolved in the gas diffusion membrane 3 and then are desorbed at the other side of the membrane under the action of the concentration difference of the gas at the two sides of the membrane, so that the quantity of the gas molecules which can enter the hydrogen sensor can be greatly controlled, and the phenomenon that the gas is queued in the gas detection unit 2 is avoided. In addition, the gas diffusion membrane 3 is as close to the working electrode 22 as possible, so that gas molecules entering the hydrogen sensor immediately undergo chemical reaction at the working electrode 22; in addition, the sealing piece 4 is arranged between the gas diffusion membrane 3 and the working electrode 22, so that the working electrode reaction air chamber 5 is formed, the fact that gas molecules entering the hydrogen sensor can only reach the working electrode 22 but not reach the counter electrode 23 and the reference electrode 24 is ensured, and the rapid and accurate stability of the whole hydrogen sensor is ensured. By using a non-porous gas diffusion membrane 3 and as small a working electrode reaction chamber 5 design as possible, a very fast response of the hydrogen sensor is enabled, which can cope with safety monitoring at the site where hydrogen is accumulated instantaneously.
The active component on the working electrode 22 may be one metal or a mixture of several metals of gold (Au), rhodium (Rh), platinum (Pt), ruthenium (Ru), palladium (Pd), iridium (Ir), silver (Ag), or the above metal or a mixture of metals supported on conductive carbon particles, that is, the above metal or the mixture of metals is supported on conductive carbon particles, wherein the conductive carbon particles may be one or a combination of several of carbon black, carbon nanotubes, or activated carbon, and preferably, the metal or the mixture of metals supported on the conductive carbon particles is used. The working electrode 22 preferably uses a porous gas diffusion electrode, and the nano-micropores on the porous gas diffusion electrode and the voids formed between the irregularly shaped conductive carbon particles carrying the metal catalyst and the voids of the conductive carbon particles themselves provide good conduction paths for hydrogen gas, so that the hydrogen gas can quickly reach the inner and outer layers of the working electrode 22 to enable all active components to function.
An oxygen storage space 6 for storing oxygen is formed below the counter electrode 23, and the volume of the oxygen storage space 6 is 0.1 to 100ml, preferably 1 to 50ml, more preferably 10 to 30ml. Since oxygen plays an indispensable role in the whole chemical reaction process, the hydrogen sensor must ensure sufficient oxygen supply during use, and the conventional electrochemical hydrogen sensor causes a reaction suspension phenomenon due to oxygen deficiency because no corresponding preventive work is performed against the oxygen supply problem. The GE company adds an oxygen diffusion channel in the product, and adds an oxygen diffusion hole on the shell on one side of the counter electrode of the hydrogen sensor to ensure the supply of oxygen, but the design is only suitable for the condition that only the working electrode can contact the gas to be detected, otherwise, the phenomenon that the gas to be detected enters the hydrogen sensor through the oxygen diffusion hole to reach the counter electrode and the reference electrode can occur, so that the whole sensor is invalid. Therefore, in the present embodiment, the oxygen storage space 6 formed below the counter electrode 23 is added so that sufficient oxygen is stored in the oxygen storage space 6 during the installation of the hydrogen sensor, and by such a design, the hydrogen sensor can be applied to any place without fear of oxygen deficiency.
In one embodiment, the electrolyte layer 21 is a solid electrolyte layer prepared from a phenolic resin sulfonic acid type film, a polystyrene sulfonic acid type film, a polytrichlorostyrene sulfonic acid type film, or a perfluorosulfonic acid type film. The working electrode 22, counter electrode 23, and reference electrode 24 can be firmly fixed to the electrolyte layer 21 by chemical methods such as deposition, hot pressing, dipping, etching, and the like.
The traditional electrochemical hydrogen sensor adopts liquid electrolyte to carry out proton transfer, so that the design encounters the condition of strong vibration, and the liquid electrolyte can splash out to be lost, thereby causing the phenomenon of failure due to insufficient mass transfer of the hydrogen sensor. Meanwhile, as the traditional electrochemical hydrogen sensor adopts a porous diffusion film, severe accidents such as night leakage, dryness and the like can occur in extreme environments such as high temperature, high humidity, low temperature, low humidity and the like of the hydrogen sensor. In the prior art, for example, the GE company sets up the humidity control unit in order to solve above-mentioned problem inside the hydrogen sensor, and the inside is filled with the inorganic salt supersaturated solution that has specific humidity to set up porous exchange membrane on the humidity control unit, make the humidity control unit can adjust the inside humidity of hydrogen sensor through porous exchange membrane. The design can increase the volume of the hydrogen sensor, and only the humidity control unit with a large enough volume can effectively control the internal humidity of the hydrogen sensor, and meanwhile, the humidity control unit has hidden danger of internal liquid leakage and the phenomenon that the humidity control unit absorbs too much water to overflow due to the overlarge ambient humidity or the phenomenon that the humidity control unit dries up due to the overlarge ambient humidity, which can cause the humidity control unit and even the whole hydrogen sensor to fail. In the embodiment, the solid electrolyte layer is adopted, and the technology of the nonporous gas diffusion membrane 3 is combined to realize the stability of the internal humidity of the hydrogen sensor, so that the hydrogen sensor can be stably applied to various extreme environments. The solid electrolyte layer is solid and has stable and reliable mass transfer performance in the humidity range of 10-90%, so that the hydrogen sensor is free from the influence of external environment change, and the hydrogen sensor can be fundamentally ensured to be applied to extremely severe conditions. In order to better ensure the performance of the hydrogen sensor, the environmental humidity in the hydrogen sensor assembly process is strictly controlled, and the hydrogen sensor is preferably assembled by adopting an environment with the RH of more than 70 percent, so that the initial humidity sealed inside the hydrogen sensor is ensured to be 50 percent RH-90 percent RH. When the hydrogen sensor is applied to the condition of less than 10% of environmental humidity, the pre-stored initial humidity inside the hydrogen sensor can ensure the mass transfer capability of the electrolyte, and the loss of the pre-stored initial humidity inside the hydrogen sensor is avoided because the gas diffusion membrane 3 used by the hydrogen sensor is a non-porous membrane with hydrophobic property.
In another embodiment, the electrolyte layer 21 is a semi-solid electrolyte layer comprising a porous substrate filled with semi-flowable capillary gel for mass transfer within the pores of the porous substrate. Wherein, the pore of the micropore of the porous substrate is 1nm-10000nm; preferably, the pores of the micropores of the porous substrate are from 10nm to 350nm; more preferably, the pores of the micropores of the porous substrate are from 30nm to 120nm. The porous substrate can be a porous ceramic plate, a porous PTFE plate, a porous e-PTFE plate or the like, and has good structural stability, supporting force, corrosion resistance and abundant micropores. Wherein, the e-PTFE is a microporous material formed by taking polytetrafluoroethylene as a raw material and puffing and stretching.
The capillary colloid comprises nano porous particles and acidic electrolyte adsorbed on the nano porous particles, and the volume ratio of the nano porous particles to the acidic electrolyte is 0.1-1.2; preferably, the volume ratio of the nano-porous particles to the acidic electrolyte is 0.3-1; more preferably, the volume ratio of the nanoporous particles to the acidic electrolyte is between 0.5 and 0.75. The particle size of the nano porous particles is 1nm-50nm; preferably, the particle size of the nanoporous particles is from 5nm to 10nm. The specific surface area of the nano porous particles is 300 square meters per gram to 2000 square meters per gram; preferably, the specific surface area of the nanoporous particles is in the range of 1200 square meters per gram to 1500 square meters per gram. The nano-porous particles are nano-porous particles with abundant micropores and larger specific surface area, and can be any one or a mixture of a plurality of silicon dioxide particles, ceramic particles and expanded polytetrafluoroethylene particles (e-PTFE particles); the acidic electrolyte can be any one or a mixture of more than one of sulfuric acid, nitric acid, phosphoric acid, benzenesulfonic acid and benzoic acid.
In the preparation process, firstly, an acidic electrolyte and nano porous particles are mixed into a colloid capillary colloid with semi-fluidity, then the porous base material and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous base material serving as a supporting framework, and the porous base material and the supporting framework of the porous base material are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The capillary colloid can be firmly fixed in the micropores of the supporting framework of the porous base material even if the hydrogen sensor is applied to occasions with strong vibration by utilizing the supporting framework structure of the porous base material, intermolecular acting force and capillary phenomenon formed by the micropores, so that the contact between an electrode and an electrolyte layer is ensured, and the electrolyte leakage phenomenon caused by vibration or environmental humidity change can be prevented, and the hydrogen sensor can be stably detected under the extreme condition of vibration.
Some of the structures and components are described below by way of specific examples, and others not described are the same as those described above.
Example 1:
the gas diffusion membrane 3 is made of polytetrafluoroethylene-perfluoropropyl vinyl ether copolymer. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 10mm, the thickness of the gas diffusion membrane 3 was 0.05mm, and the volume of the oxygen storage space was 20ml. The electrolyte layer 21 is a solid electrolyte layer made of a phenolic resin sulfonic acid type film, and the working electrode 22, the counter electrode 23, and the reference electrode 24 are firmly fixed on the electrolyte layer 21 by deposition. As shown in fig. 2, the response time of the hydrogen sensor in the embodiment is only 13s, and the response voltage is more than 180 mV; in contrast, the response time of the city7HYE in the prior art is 93s, and the response voltage is approximately 140mV, so that the response time of the hydrogen sensor in the embodiment is very short, the response voltage is high, and the detection result is rapid, accurate and reliable. As shown in fig. 3, under extreme conditions, the response time of the hydrogen sensor in this embodiment is less than 20s at a high temperature of 60 ℃ and a high humidity of 90% rh, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected, while the city7HYE hydrogen sensor in the prior art does not respond basically, so that the hydrogen sensor fails. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 2:
the gas diffusion membrane 3 is made of polytetrafluoroethylene. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 50mm, the thickness of the gas diffusion membrane 3 was 0.1mm, and the volume of the oxygen storage space was 30ml. The electrolyte layer 21 is a solid electrolyte layer made of a polystyrene sulfonic acid type film, and the working electrode 22, the counter electrode 23, and the reference electrode 24 are firmly fixed on the electrolyte layer 21 by deposition. The response time of the hydrogen sensor in the embodiment is 15s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 3:
the gas diffusion membrane 3 is made of polytetrafluoroethylene. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 0.1mm, the thickness of the gas diffusion membrane 3 was 0.005mm, and the volume of the oxygen storage space was 10ml. The electrolyte layer 21 is a semi-solid electrolyte layer, which comprises a porous ceramic plate, wherein the pores of the micropores of the porous ceramic plate are 30nm-120nm, and semi-flowable capillary colloid for mass transfer is filled in the micropores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 0.5, the particle size of the silicon dioxide particles is 5nm-10nm, and the specific surface area of the silicon dioxide particles is about 1300 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 14s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 4:
the gas diffusion membrane 3 is made of polyimide. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 0.01mm, the thickness of the gas diffusion membrane 3 was 0.05mm, and the volume of the oxygen storage space was 1ml. The electrolyte layer 21 is a semi-solid electrolyte layer including a porous PTFE sheet having pores of 10nm to 150nm and having semi-fluid capillary gel filled in the pores for mass transfer. Wherein the capillary colloid comprises ceramic particles, nitric acid is adsorbed on the ceramic particles, the volume ratio of the ceramic particles to the nitric acid is 0.75, the particle size of the ceramic particles is 5nm-30nm, and the specific surface area of the ceramic particles is about 1200 square meters per gram. Firstly, nitric acid and ceramic particles are mixed into colloid capillary colloid with semi-fluidity, then the porous PTFE plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous PTFE plate serving as a supporting framework, and the porous PTFE plate and the supporting framework of the porous PTFE plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The hydrogen sensor in the embodiment has response time of 17s, response voltage of more than 180mV, and rapid, accurate and reliable detection result. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 5:
the gas diffusion membrane 3 is made of polyvinylidene fluoride. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 100mm, the thickness of the gas diffusion membrane 3 was 0.01mm, and the volume of the oxygen storage space was 50ml. The electrolyte layer 21 is a semi-solid electrolyte layer including a porous e-PTFE sheet having pores of 1nm to 100nm, and semi-flowable capillary gel for mass transfer is filled in the pores of the porous e-PTFE sheet. Wherein the capillary colloid comprises e-PTFE particles, phosphoric acid is adsorbed on the e-PTFE particles, the volume ratio of the e-PTFE particles to the phosphoric acid is 0.1, the particle size of the e-PTFE particles is 1nm-10nm, and the specific surface area of the e-PTFE particles is about 2000 square meters per gram. Firstly, mixing phosphoric acid and e-PTFE particles to form a colloid capillary colloid with semi-fluidity, then combining a porous e-PTFE plate with the capillary colloid with semi-fluidity to enable the capillary colloid with semi-fluidity to completely fill micropores of the porous e-PTFE plate serving as a supporting framework, and firmly combining the porous e-PTFE plate and the supporting framework into a whole through intermolecular forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 16s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 6:
the gas diffusion membrane 3 is made of silicone rubber. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 100mm, the thickness of the gas diffusion membrane 3 was 0.001mm, and the volume of the oxygen storage space was 100ml. The electrolyte layer 21 is a semi-solid electrolyte layer, which comprises a porous ceramic plate, wherein the pores of the micropores of the porous ceramic plate are 200nm-350nm, and semi-flowable capillary colloid for mass transfer is filled in the micropores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 0.1, the particle size of the silicon dioxide particles is 10nm-50nm, and the specific surface area of the silicon dioxide particles is about 1500 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 15s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 7:
the gas diffusion membrane 3 is made of polytetrafluoroethylene-hexafluoropropylene copolymer. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 0.01mm, the thickness of the gas diffusion membrane 3 was 0.01mm, and the volume of the oxygen storage space was 0.1ml. The electrolyte layer 21 is a semi-solid electrolyte layer, which comprises a porous ceramic plate, wherein the pores of the micropores of the porous ceramic plate are 350nm-1000nm, and semi-flowable capillary colloid for mass transfer is filled in the micropores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 0.1, the particle size of the silicon dioxide particles is 40nm-50nm, and the specific surface area of the silicon dioxide particles is about 300 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 18s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 8:
the gas diffusion membrane 3 is made of a polyethylene-tetrafluoroethylene copolymer. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 2mm, the thickness of the gas diffusion membrane 3 was 0.1mm, and the volume of the oxygen storage space was 5ml. The electrolyte layer 21 is a semi-solid electrolyte layer including a porous ceramic plate having pores of 1000nm to 10000nm, and semi-flowable capillary gel for mass transfer is filled in the pores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 0.3, the particle size of the silicon dioxide particles is 10nm-30nm, and the specific surface area of the silicon dioxide particles is about 1000 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The hydrogen sensor in the embodiment has response time of 17s, response voltage of more than 180mV, and rapid, accurate and reliable detection result. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 9:
the gas diffusion membrane 3 is made of polytetrafluoroethylene. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 2mm, the thickness of the gas diffusion membrane 3 was 0.1mm, and the volume of the oxygen storage space was 5ml. The electrolyte layer 21 is a semi-solid electrolyte layer, which comprises a porous ceramic plate, wherein the pores of the micropores of the porous ceramic plate are 30nm-120nm, and semi-flowable capillary colloid for mass transfer is filled in the micropores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 1, the particle size of the silicon dioxide particles is 5nm-10nm, and the specific surface area of the silicon dioxide particles is about 1300 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 18s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
Example 10:
the gas diffusion membrane 3 is made of polytetrafluoroethylene. The distance between the working electrode 22 and the opposite sides of the gas diffusion membrane 3 was 2mm, the thickness of the gas diffusion membrane 3 was 0.1mm, and the volume of the oxygen storage space was 5ml. The electrolyte layer 21 is a semi-solid electrolyte layer, which comprises a porous ceramic plate, wherein the pores of the micropores of the porous ceramic plate are 30nm-120nm, and semi-flowable capillary colloid for mass transfer is filled in the micropores of the porous ceramic plate. The capillary colloid comprises silicon dioxide particles, sulfuric acid is adsorbed on the silicon dioxide particles, the volume ratio of the silicon dioxide particles to the sulfuric acid is 1.2, the particle size of the silicon dioxide particles is 5nm-10nm, and the specific surface area of the silicon dioxide particles is about 1300 square meters per gram. Firstly, sulfuric acid and silicon dioxide particles are mixed into colloid capillary colloid with semi-fluidity, then the porous ceramic plate and the capillary colloid with semi-fluidity are combined together, so that the capillary colloid with semi-fluidity completely fills micropores of the porous ceramic plate serving as a supporting framework, and the porous ceramic plate and the supporting framework of the porous ceramic plate are firmly combined into a whole through intermolecular acting forces such as Van der Waals force. The response time of the hydrogen sensor in the embodiment is 16s, the response voltage is more than 180mV, and the detection result is quick, accurate and reliable. Under extreme conditions, the high temperature is 60 ℃, the high humidity is 90% RH, the response time of the hydrogen sensor in the embodiment is less than 20s, and the response voltage is still kept above 180mV, so that the hydrogen sensor is still in an effective state, and can be rapidly and accurately detected. The performance of the hydrogen sensor in the embodiment is basically unchanged after vibration after the performance test of the hydrogen sensor before and after the vibration experiment is performed.
It will be appreciated that modifications and variations will be apparent to those skilled in the art from the above description, and it is intended to be within the scope of the invention as defined in the appended claims.
Claims (7)
1. The hydrogen sensor for rapidly detecting low-concentration hydrogen comprises a shell (1), wherein a gas detection unit (2) is arranged in the shell (1), the gas detection unit (2) comprises an electrolyte layer (21), and a working electrode (22), a counter electrode (23) and a reference electrode (24) which are integrated with the electrolyte layer (21), and the hydrogen sensor is characterized in that a gas diffusion film (3) is arranged on one side, facing the working electrode (22), in the shell (1), of the shell (1), a working electrode reaction air chamber (5) for reacting hydrogen on the working electrode (22) is formed by sealing the gas diffusion film (3) and the working electrode (22) through a sealing piece (4), and the gas diffusion film (3) is a gas diffusion film with a non-porous structure, and the electrolyte layer (21) is a solid electrolyte layer or a semi-solid electrolyte layer;
two paths are formed in the gas detection unit (2), including a reaction path and an output path, wherein the reaction path is composed of a working electrode (22) and a counter electrode (23); the output passage consists of a working electrode (22) and a reference electrode (24);
the distance between the two opposite sides of the working electrode (22) and the gas diffusion film (3) is 10mm, the thickness of the gas diffusion film (3) is 0.05mm, an oxygen storage space (6) for storing oxygen is formed below the counter electrode (23), and the volume of the oxygen storage space (6) is 20ml.
2. The hydrogen sensor according to claim 1, wherein the gas diffusion membrane (3) is a gas diffusion membrane made of any one or a mixture of several of polytetrafluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-perfluoropropyl vinyl ether copolymer, polyethylene-tetrafluoroethylene copolymer, polyimide, silicone rubber, fluorinated silicone rubber.
3. Hydrogen sensor according to claim 1, characterized in that the housing (1) comprises a body (11) with an opening and a cover (12) covering the opening of the body (11), a sealing ring (13) is arranged on the side wall of the cover (12), and a notch (14) matching with the sealing ring (13) is formed on the inner wall of the opening of the housing (1).
4. The hydrogen sensor according to claim 1, characterized in that the working electrode (22) is located on one side of the electrolyte layer (21), the counter electrode (23) and the reference electrode (24) are located on the other side of the electrolyte layer (21) and the counter electrode (23) and the reference electrode (24) are juxtaposed on the other side of the electrolyte layer (21).
5. Hydrogen sensor according to claim 1, characterized in that the initial humidity inside the housing (1) is 50-90% rh.
6. The hydrogen sensor according to claim 1, characterized in that the electrolyte layer (21) is a solid electrolyte layer prepared from a phenol resin sulfonic acid type film, a polystyrene sulfonic acid type film, a polytrichlorostyrene sulfonic acid type film or a perfluorosulfonic acid type film.
7. Hydrogen sensor according to claim 1, characterized in that the electrolyte layer (21) is a semi-solid electrolyte layer comprising a porous substrate, inside the micropores of which a semi-fluid capillary gel for mass transfer is filled; the capillary colloid comprises nano porous particles and acidic electrolyte adsorbed on the nano porous particles, and the volume ratio of the nano porous particles to the acidic electrolyte is 0.1-1.2.
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