CN206470229U - A kind of hydrogen gas sensor for quick detection low-concentration hydrogen - Google Patents
A kind of hydrogen gas sensor for quick detection low-concentration hydrogen Download PDFInfo
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- CN206470229U CN206470229U CN201621457485.8U CN201621457485U CN206470229U CN 206470229 U CN206470229 U CN 206470229U CN 201621457485 U CN201621457485 U CN 201621457485U CN 206470229 U CN206470229 U CN 206470229U
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Abstract
The utility model is related to a kind of hydrogen gas sensor for quick detection low-concentration hydrogen, including housing, gas detection cell is installed in housing, gas detection cell includes dielectric substrate and the working electrode being combined into one with dielectric substrate, to electrode and reference electrode, gas diffusion membrane is installed towards the side of working electrode in housing, the working electrode reaction air chamber to be formed and be reacted on the working electrode (s for hydrogen is sealed between gas diffusion membrane and working electrode by seal, gas diffusion membrane is the gas diffusion membrane of non-porous structure, dielectric substrate is solid-state electrolyte layer or semisolid dielectric substrate.Hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen has very quickly response, it can tackle and gather the safety monitoring in the place of hydrogen in moment, the hydrogen monitoring in the fields such as vehicle, power plant, nuclear power can be widely used in the hydrogen of the detection low concentration of fast accurate under harsh environment.
Description
Technical field
The utility model is related to the technical field of hydrogen gas sensor, and it is low to be used for quick detection more specifically to one kind
The hydrogen gas sensor of concentration hydrogen.
Background technology
Current hydrogen detection method has following several：
(1) semiconductor-type sensors：Detected by the change of semiconductor material resistance before and after contact hydrogen, it is excellent
It is fast that point is in response to speed；Have the disadvantage the hydrogen detection that can only carry out percentage concentrations above, and semiconductor element long-term work
The failure such as easily occur fusing at high temperature；Shock resistance is poor simultaneously, and can have the phenomenon of organosilicon poisoning；
(2) catalytic combustion type sensor：By the high temperature that detecting element is heated to several Baidu so that hydrogen is sent out above
Raw combustion reaction, detects the size of current produced, and advantage and disadvantage are essentially identical with semiconductor-type sensors；
(3) electrochemical transducer[sensor：Using the corresponding product of British city technology company as representative, pass through constant potentiometric electrolysis
To carry out the detection of hydrogen, advantage is can to detect PPM grades of hydrogen content, has the disadvantage not providing fast under emergency case
Speed diagnosis, and is not suitable for the extreme environments such as hot and humid, low temperature and low humidity, the life-span is shorter, especially longevity in the presence of a harsh environment
Life is even more limited；
(4) fuel cell formula sensor：Using GE companies and DART companies of Britain as Typical Representative, pass through micro fuel cell
To realize the detection of gas, the sensor that the former produces has long lifespan, goes for the inferior outstanding advantage of extreme environment, but
It is to sacrifice the detection speed of sensor while above-mentioned advantage is obtained, so high concentration may be accumulated by being not suitable for moment
The place of hydrogen；The sensor response speed that the latter is produced is very fast, but can not also be suitable under harsh environment；
(5) thin-film capacitor French sensor：It is rapid with response using the corresponding product of H2Scan companies as Typical Representative,
It is applicable under adverse circumstances, the outstanding advantage such as service life length, but this kind of sensor can not carry out the inspection of low-concentration hydrogen
Survey.
Utility model content
The purpose of this utility model is to provide a kind of hydrogen gas sensor for quick detection low-concentration hydrogen, solved
Hydrogen gas sensor of the prior art can not be the problem of quick detection low-concentration hydrogen under critical conditions.
The utility model solves the technical scheme that is used of technical problem：It is a kind of for quick detection low-concentration hydrogen
Hydrogen gas sensor, including housing, are provided with gas detection cell in the housing, and the gas detection cell includes electrolyte
Layer and the working electrode being combined into one with the dielectric substrate, to electrode and reference electrode, towards described in the housing
The side of working electrode is provided with gas diffusion membrane, is sealed between the gas diffusion membrane and the working electrode by seal
Form the working electrode reacted for hydrogen on the working electrode and react air chamber, the gas diffusion membrane is non-porous knot
The gas diffusion membrane of structure, the dielectric substrate is solid-state electrolyte layer or semisolid dielectric substrate.
In hydrogen gas sensor of the present utility model, between the working electrode both sides relative with the gas diffusion membrane
Distance be 0.01mm-100mm.
In hydrogen gas sensor of the present utility model, the thickness of the gas diffusion membrane is 0.001mm-0.1mm.
In hydrogen gas sensor of the present utility model, the gas diffusion membrane be by polytetrafluoroethylene (PTFE), gathered PVF, it is poly-
Tetrafluoraoethylene-hexafluoropropylene copolymer, the vinyl ether copolymers of polytetrafluoroethylene (PTFE)-perfluor third, polyethylene-TFE copolymer,
The gas diffusion membrane that any one or a few mixture formed in polyimides, silicon rubber, fluorination silicon rubber is made.
In hydrogen gas sensor of the present utility model, the housing includes main body and lid with opening and is located at the main body
Opening at lid, the inwall being provided with sealing ring, the opening of the housing on the side wall of the lid is formed with and institute
State the recess that sealing ring matches.
In hydrogen gas sensor of the present utility model, the sealing ring is the sealing ring being made up of fluorubber or silicon rubber.
In hydrogen gas sensor of the present utility model, the seal is gasket seal.
In hydrogen gas sensor of the present utility model, the gasket seal is the sealing gasket being made up of fluorubber or silicon rubber
Piece.
In hydrogen gas sensor of the present utility model, the working electrode is located at the side of the dielectric substrate, described right
Electrode and reference electrode be located at the opposite side of the dielectric substrate and it is described to electrode and reference electrode in the dielectric substrate
Opposite side is set up in parallel.
In hydrogen gas sensor of the present utility model, the storage oxygen space formed below for being used to store up oxygen to electrode,
The volume in the storage oxygen space is 0.1-100ml.
Implement the hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen, have the advantages that：
Hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen has very quickly response, can tackle in wink
Between accumulation hydrogen place safety monitoring, can be suitable extensively with the hydrogen of the detection low concentration of fast accurate under harsh environment
Hydrogen for fields such as vehicle, power plant, nuclear powers is monitored.
Brief description of the drawings
Fig. 1 is the structural representation of the hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen；
Fig. 2 is the hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen and hydrogen of the prior art
The contrast curve of the response time of sensor；
Fig. 3 is the hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen and hydrogen of the prior art
The curve map of sensor performance comparison under extreme conditions.
Embodiment
With reference to the accompanying drawings and examples, to the hydrogen gas sensor of the present utility model for quick detection low-concentration hydrogen
Structure and working principle be described further：
In description of the present utility model, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " on ", " under ",
"front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom ", " interior ", " outer ", " clockwise ", " counterclockwise " etc. are indicated
Orientation or position relationship are, based on orientation shown in the drawings or position relationship, to be for only for ease of description the utility model and simplification
Description, rather than indicate or imply that the device or element of meaning must have specific orientation, with specific azimuth configuration and behaviour
Make, therefore it is not intended that to limitation of the present utility model.
As shown in figure 1, the hydrogen gas sensor for quick detection low-concentration hydrogen includes housing 1, housing 1, which includes having, to be opened
The main body 11 and lid of mouth are located on the lid 12 at the opening of main body 11, the side wall of lid 12 and are provided with sealing ring 13, housing 1
Inwall at opening is formed with the recess 14 matched with sealing ring 13, sealing ring 13 be by fluorubber or silicon rubber be made it is close
Seal.Can be with when hydrogen gas sensor needs to be applied to the place that power plant, nuclear power etc. require to the shielding of hydrogen gas sensor
There is the housing 1 of shielding properties using copper, aluminium, stainless steel etc.；When need be applied to general industry place, vehicle and hand-held
The housing 1 of the materials such as PP, ABS, PC, PTFE, POM can be used when in instrument, to reduce the cost of whole hydrogen gas sensor.
Gas detection cell 2 is installed in housing 1, gas detection cell 2 includes dielectric substrate 21 and and electrolyte
Working electrodes 22 that layer 21 is combined into one, to electrode 23 and reference electrode 24, wherein working electrode 22 is located at dielectric substrate 21
Side, the opposite side of dielectric substrate 21 is located to electrode 23 and reference electrode 24 and to electrode 23 and reference electrode 24 in electrolysis
The opposite side of matter layer 21 is set up in parallel.Be provided with outside of the housing 1 away from one end at opening for docked with pcb board
One contact pin 15, the second contact pin 16 and the 3rd contact pin 17, working electrode 22 are electrically connected by working electrode lead 25 with the first contact pin 15
Connect, to electrode 23 by being electrically connected to contact conductor 26 with the second contact pin 16, reference electrode 24 by reference electrode lead 27 with
3rd contact pin 17 is electrically connected.Whole hydrogen gas sensor is fixed on PCB by the first contact pin 15, the second contact pin 16, the 3rd contact pin 17
On plate.Working electrode 22 is the place that electrochemical reaction occurs under test gas, is that electrification occurs for the oxygen in environment to electrode 23
The place of reaction is learned, reference electrode 24 plays stabilizing potential zero point, and dielectric substrate 21 plays a part of to transmit proton, work electricity
Pole 22, it electrode 23 and reference electrode 24 must fully be contacted with dielectric substrate 21 respectively could keep the patency of system mass transfer
And reactivity worth.Two paths, including reaction path and output channel, reaction therein are formed in the gas detection cell
Path is constituted by working electrode 22 and to electrode 23, the under test gas (i.e. hydrogen) that is chemically reacted on working electrode 22 and
The oxygen chemically reacted on to electrode 23 together form a complete chemical reaction so that reaction can persistently enter
Row goes down；Output channel is made up of working electrode 22 and reference electrode 24, due to that can go out to electrode 23 during long reaction
The phenomenons such as now drift, polarization, now if output services electrode 22 can cause whole hydrogen to the electrical potential difference of electrode 23 relatively
The drift of gas sensor, it is so introduce reference electrode 24, the potential of reference electrode 24 is stable in a fixed value, generally this
Potential is located at excitation voltage when under test gas chemically reacts on working electrode 22, can so improve to greatest extent
The detectability of working electrode 22.Chemical reaction is lasting occur during, output is working electrode 22 relative to reference
The electrical potential difference of electrode 24, can thus avoid the influence due to polarizing electrode 23 to whole hydrogen gas sensor.
Gas diffusion membrane 3 is installed towards the side of working electrode 22 in housing 1, specifically, in the lid 12 of housing 1
Gas diffusion membrane 3 is installed towards the side of working electrode 22.It is close by seal 4 between gas diffusion membrane 3 and working electrode 22
Envelope, which is formed, is used for the working electrode reaction air chamber 5 that hydrogen reacts on working electrode 22, and seal 4 is preferably sealing gasket
Piece, the thickness of gasket seal is preferably 0.01-10mm.Can also be in other embodiments Seal Oil, wherein gasket seal can
To use fluorubber material and silicon rubber material, preferably fluorubber material.Working electrode 22 is set close to gas diffusion membrane 3, work
Make the distance between both sides relative with gas diffusion membrane 3 of electrode 22 for 0.01mm-100mm；Preferably, working electrode 22 and gas
The distance between relative both sides of body diffusion barrier 3 are 0.1mm-50mm.Gas diffusion membrane 3 is the gas diffusion membrane of non-porous structure,
The thickness of gas diffusion membrane 3 is 0.001mm-0.1mm；Preferably, the thickness of gas diffusion membrane 3 is 0.01mm-0.05mm.Gas
Diffusion barrier 3 is by polytetrafluoroethylene (PTFE), gathered PVF, polytetrafluoroethylene (PTFE)-hexafluoropropylene copolymer, polytetrafluoroethylene (PTFE)-perfluor third
Vinyl ether copolymers, polyethylene-TFE copolymer, polyimides, silicon rubber, fluorination silicon rubber in any one or it is several
Plant the gas diffusion membrane that the mixture formed is made.
What the response speed of sensor was represented is the ability that sensor contacts reach balance to output after under test gas.For
For one sensor, its output reaches that balance is not as chemical reaction and stopped, but because under test gas is from extraneous ring
The speed that sensor internal is entered in border is equal with the speed that it is consumed at working electrode.Traditional electrochemical hydrogen sensing
Diffusion barrier on device is generally using the perforated membrane with hydrophobicity performance, and the film is that porous and traditional electrochemical hydrogen is passed
Gas detection cell in sensor to electrode, reference electrode and working electrode the lower section of porous diffusion barrier from top to bottom according to
Secondary design, therefore working electrode and the distance between diffusion barrier are larger, and then prevent from being bonded at during electrolyte leakage on diffusion barrier and lead
Cause diffusion barrier failure.The hydrophobicity performance of diffusion barrier can ensure that sensor is not influenceed by extreme cases such as extraneous water droplet adhesions；
Porous on diffusion barrier can ensure that gas molecule as much as possible is straightway and enter sensor internal, so as to improve
The detection accuracy of sensor；But it is due to have that numerous gas molecules can enter sensor internal and gas detection is single
The respond of member is limited to be will result in numerous molecules and is queued up at gas detection cell the phenomenon chemically reacted, while by
In larger distance between diffusion barrier and working electrode, this just undoubtedly extends the response time of sensor.In the utility model
Using non-porous gas diffusion membrane 3, it is desirable to must be by the mistake of dissolving-desorption by the gas molecule of this layer of gas diffusion membrane 3
Journey is realized, that is, gas molecule is first dissolved in gas diffusion membrane 3 again in the presence of film both sides gas concentrations difference in film
Opposite side be desorbed out, thus can greatly control can enter hydrogen gas sensor inside gas molecule quantity,
Avoid the occurrence of the phenomenon that gas is queued up in gas detection cell 2.Other gas diffusion membrane 3 presses close to working electrode 22 as far as possible,
So that being chemically reacted at once in working electrode 22 into the gas molecule inside hydrogen gas sensor；In addition, gas diffusion membrane 3
Seal 4 is provided between working electrode 22, working electrode reaction air chamber 5 is formd, it is ensured that enter in hydrogen gas sensor
The gas molecule in portion can only reach working electrode 22 and can not reach to electrode 23 and reference electrode 24, it is ensured that whole hydrogen is passed
Sensor detects fast and accurately stability.By using non-porous gas diffusion membrane 3 and working electrode reaction gas as small as possible
Room 5, which is designed, causes hydrogen gas sensor to have very quickly response, can tackle the safety prison that the place of hydrogen is gathered in moment
Survey.
Wherein, the active component on working electrode 22 can be golden (Au), rhodium (Rh), platinum (Pt), ruthenium (Ru), palladium (Pd),
Iridium (Ir), the mixture of a kind of metal in silver-colored (Ag) or several metals or support in above-mentioned on conductive carbon particle
Metal or metal mixture, i.e., above-mentioned metal or metal mixture are supported on conductive carbon particle, and conductive carbon particle therein can
To be one or more of combinations in carbon black, CNT or activated carbon, it is preferred to use support in the gold on conductive carbon particle
Category or metal mixture.The nanometer that working electrode 22 is preferably used on porous gas diffusive electrode, porous gas diffusive electrode is micro-
Hole and it is supported with the space formed between the conductive carbon particle in irregular shape of metallic catalyst and conductive carbon particle sheet
The space of body all provides good pathway for hydrogen so that hydrogen can quickly reach the ectonexine of working electrode 22 with
All active components are made to play a role.
In the storage oxygen space 6 formed below for being used to store up oxygen to electrode 23, the volume in the storage oxygen space 6 is 0.1-
100ml, preferably 1-50ml, more preferably 10-30ml.Due to oxygen played in whole chemical reaction process it is indispensable
Effect, thus hydrogen gas sensor must assure that in use abundance oxygen supply, Conventional electrochemical hydrogen gas sensor by
Cause to react break-off phenomenon due to anoxic in not being directed to the corresponding prevention work of oxygen supply problem progress.GE companies produce at it
Oxygen diffusion admittance is additionally arranged in product, increases oxygen diffusion holes on housing of the hydrogen gas sensor to electrode one side to ensure oxygen
Supply, but such design is suitable only for applying and can touch the situation of under test gas in only working electrode, otherwise can
There is under test gas and enter inside hydrogen gas sensor the phenomenon reached to electrode and reference electrode by oxygen diffusion holes, so as to lead
Cause whole sensor failure.Therefore, in the present embodiment, the storage oxygen space 6 formed below to electrode 23 is added so that in hydrogen
Just there is enough oxygen to be stored in storage oxygen space 6 in gas sensor installation process, by such design hydrogen is passed
The problem of sensor can apply in any place without worrying anoxic.
In one embodiment, dielectric substrate 21 be solid-state electrolyte layer, solid-state electrolyte layer be phenolic resin sulfonic acid type film,
The solid-state electrolyte layer of polystyrene sulfonic acid type film, poly- trichlorostyrene sulfonic acid type film or perfluorosulfonic acid type film preparation.Work electricity
Pole 22, electricity can be firmly fixed to by chemical methodes such as deposition, hot pressing, dipping, etchings to electrode 23 and reference electrode 24
Solve on matter layer 21.
Conventional electrochemical hydrogen gas sensor carries out proton transfer using liquid electrolyte, and so design runs into vibrations and compared
Strong situation, liquid electrolyte can sputter to lose, so as to cause the hydrogen gas sensor to occur that mass transfer is not enough and failure shows
As.Simultaneously because Conventional electrochemical hydrogen gas sensor uses porous diffusion barrier, cause hydrogen gas sensor in high temperature, high humidity, low
The extreme environments such as temperature, low humidity occur in the dead of night and the serious accident such as dry.In the prior art, it is above-mentioned to solve such as GE companies
Problem is set inside hydrogen gas sensor controls wet unit, inorganic salts supersaturated solution of the inside filling with specified moisture, and
Control and porous exchange membrane is set on wet unit so that the wet unit of control can adjust wet inside hydrogen gas sensor by porous exchange membrane
Degree.Such design can increase the volume of hydrogen gas sensor, and the only wet unit of the sufficiently large control of volume can just be achieved effective control
, there is the hidden danger of internal liquid leakage and because environmental wet is spent with the wet unit of time control in the effect of hydrogen gas sensor interior humidity
It is big that to cause to control wet unit water suction excessive and the phenomenon overflowed occur or because ambient humidity is too low and the wet unit of control occurs and dries up
Phenomenon, these can all to control wet unit or even the failure of whole hydrogen gas sensor.And in the present embodiment, by using solid-state
Dielectric substrate, realizes the stabilization of hydrogen gas sensor interior humidity, it is ensured that hydrogen with reference to the technology of non-porous gas diffusion membrane 3
What sensor can be stablized is applied to various extreme environments.Because solid-state electrolyte layer is solid in itself, and 10%~
All there is reliable and stable mass-transfer performance so that the shadow that hydrogen gas sensor changes from external environment in 90% humidity range
Ring, fundamentally ensure that hydrogen gas sensor can apply to it is exceedingly odious under the conditions of.In order to preferably ensure hydrogen gas sensor
Performance, the ambient humidity in strict control hydrogen gas sensor assembling process, it is preferred to use more than 70%RH environment carries out hydrogen
The assembling of gas sensor, it is ensured that it is 50%RH-90%RH to seal the initial humidity inside hydrogen gas sensor up for safekeeping.Work as hydrogen gas sensor
When being applied to less than under conditions of 10% ambient humidity, the initial humidity that prestores inside hydrogen gas sensor can ensure electrolyte
Mass transfer ability, and because the gas diffusion membrane 3 used in hydrogen gas sensor is non-porous, and there is the film of hydrophobicity performance, it is to avoid
The loss of the initial humidity prestored inside hydrogen gas sensor.
In another embodiment, dielectric substrate 21 is semisolid dielectric substrate, and semisolid dielectric substrate includes porous substrate,
The semimobile capillary colloid for mass transfer is filled with the micropore of porous substrate.Wherein, the hole of the micropore of porous substrate
Gap is 1nm-10000nm；Preferably, the hole of the micropore of porous substrate is 10nm-350nm；It is highly preferred that porous substrate is micro-
The hole in hole is 30nm-120nm.Porous substrate can be porous ceramic plate, porous PTFE plate or porous e-PTFE plates etc., and this is more
Hole base material has good structural stability, support force, corrosion resistance and abundant micropore.Wherein e-PTFE refers to poly- four
PVF is the microporous materials that raw material is formed through expanded stretching.
Capillary colloid includes the acidic electrolysis bath of nanoporous particles and absorption on nanoporous particles, nanoporous
The volume ratio of grain and acidic electrolysis bath is 0.1-1.2；Preferably, the volume ratio of nanoporous particles and acidic electrolysis bath is 0.3-
1；It is highly preferred that the volume ratio of nanoporous particles and acidic electrolysis bath is 0.5-0.75.The particle diameter of nanoporous particles is
1nm-50nm；Preferably, the particle diameter of nanoporous particles is 5nm-10nm.The specific surface area of nanoporous particles is 300 squares
Rice/gram -2000 meters squared per grams；Preferably, the specific surface area of nanoporous particles be -1500 square metres of 1200 meters squared per gram/
Gram.Nanoporous particles are the nanoporous particles with abundant micropore and large specific surface area, can be silica
Any one or a few mixture in grain, ceramic particle, expanded PTFE particle (e-PTFE particles)；Acidic electrolysis
Liquid can be any one or a few the mixed liquor in sulfuric acid, nitric acid, phosphoric acid, benzene sulfonic acid, benzoic acid.
In preparation process, acidic electrolysis bath and nanoporous particles are mixed into semimobile colloidal first
Capillary colloid, then porous substrate is allowed semimobile capillary glue with being combined together with semimobile capillary colloid
Body is fully filled with the micropore of the porous substrate as support frame, and passes through Van der Waals force equimolecular intermolecular forces and porous substrate
Support frame be firmly combined as a whole.Utilize support framework structure, intermolecular force and the micropore institute of porous substrate
The capillarity of formation is wet to lock, can also jail compared with the occasion capillary colloid of strong motion even if hydrogen gas sensor is applied into presence
Solid be fixed in the micropore of the support frame of porous substrate, not only ensure that contact of the electrode with dielectric substrate but can prevent because
Electrolyte leakage phenomenon caused by vibrations or ambient humidity change so that hydrogen gas sensor can also under the extreme condition of vibrations
Stable detection.
Part-structure and composition are illustrated below by specific embodiment, it is other it is unaccounted then with it is foregoing illustrated
Structure and composition it is identical.
Embodiment 1：
Gas diffusion membrane 3 is made up of the vinyl ether copolymers of polytetrafluoroethylene (PTFE)-perfluor third.Working electrode 22 expands with gas
It is 10mm to dissipate the distance between relative both sides of film 3, and the thickness of gas diffusion membrane 3 is 0.05mm, and the volume in storage oxygen space is
20ml.Dielectric substrate 21 is solid-state electrolyte layer, and the solid-state electrolyte layer is the solid-state electricity being made up of phenolic resin sulfonic acid type film
Solve matter layer, working electrode 22, electrode 23 and reference electrode 24 are firmly fixed on dielectric substrate 21 by deposition.Such as Fig. 2
It is shown, the hydrogen gas sensor response time only 13s in the present embodiment, response voltage is in more than 180mV；And prior art
City7HYE response time 93s, response voltage is probably in 140mV, it can be seen that the response of the hydrogen gas sensor in the present embodiment
Time is very short, and response voltage is high, therefore testing result is quick and precisely reliable.As shown in figure 3, under extreme conditions, 60 DEG C of high temperature,
The hydrogen gas sensor response time in high humidity 90%RH, the present embodiment is less than 20s, and response voltage stills remain in more than 180mV,
Therefore effective state is still kept, can be fast and accurately detected, and city7HYE hydrogen of the prior art is sensed
Device is not responding to cause failure substantially.And the hydrogen gas sensor in the present embodiment carries out the performance test before and after vibrations experiment, pass through
Hydrogen gas sensor test performance after vibrations in the present embodiment is basically unchanged.
Embodiment 2：
Gas diffusion membrane 3 is made up of polytetrafluoroethylene (PTFE).Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance be 50mm, the thickness of gas diffusion membrane 3 is 0.1mm, and the volume in storage oxygen space is 30ml.Dielectric substrate 21 is solid-state electricity
Matter layer is solved, the solid-state electrolyte layer is the solid-state electrolyte layer being made up of polystyrene sulfonic acid type film, working electrode 22, to electrode
23 and reference electrode 24 by deposition be firmly fixed on dielectric substrate 21.The hydrogen gas sensor response time in the present embodiment
15s, response voltage is in more than 180mV, and testing result is quick and precisely reliable.Under extreme conditions, 60 DEG C of high temperature, high humidity 90%
The hydrogen gas sensor response time in RH, the present embodiment is less than 20s, and response voltage stills remain in more than 180mV, therefore still
Effective state is kept, can fast and accurately be detected.And the hydrogen gas sensor in the present embodiment is carried out before vibrations experiment
Performance test afterwards, the hydrogen gas sensor test performance after vibrations in the present embodiment is basically unchanged.
Embodiment 3：
Gas diffusion membrane 3 is made up of polytetrafluoroethylene (PTFE).Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance be 0.1mm, the thickness of gas diffusion membrane 3 is 0.005mm, and the volume in storage oxygen space is 10ml.Dielectric substrate 21 is half
Solid-state electrolyte layer, the semisolid dielectric substrate includes porous ceramic plate, and the hole of the micropore of porous ceramic plate is 30nm-
120nm, is filled with the semimobile capillary colloid for mass transfer in the micropore of porous ceramic plate.Wherein, capillary colloid bag
Silica dioxide granule is included, sulfuric acid is adsorbed on silica dioxide granule, the volume ratio of silica dioxide granule and sulfuric acid is 0.5, dioxy
The particle diameter of silicon carbide particle is 5nm-10nm, and the specific surface area of silica dioxide granule is about 1300 meters squared per grams.First sulfuric acid with
Silica dioxide granule is mixed into the capillary colloid with semimobile colloidal, then porous ceramic plate with having half mobility
Capillary colloid be combined together, allow semimobile capillary colloid be fully filled with as support frame porous ceramic plate it is micro-
Hole, and be firmly combined as a whole by the support frame of Van der Waals force equimolecular intermolecular forces and porous ceramic plate.This implementation
Hydrogen gas sensor response time 14s in example, response voltage is in more than 180mV, and testing result is quick and precisely reliable.In extreme bar
Under part, 60 DEG C of high temperature, high humidity 90%RH, the hydrogen gas sensor response time in the present embodiment is less than 20s, and response voltage is still protected
Hold in more than 180mV, therefore still keep effective state, can fast and accurately be detected.And the hydrogen in the present embodiment
Gas sensor carries out the performance test before and after vibrations experiment, the hydrogen gas sensor test performance base after vibrations in the present embodiment
This is constant.
Embodiment 4：
Gas diffusion membrane 3 is made up of polyimides.Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance is 0.01mm, and the thickness of gas diffusion membrane 3 is 0.05mm, and the volume in storage oxygen space is 1ml.Dielectric substrate 21 is semisolid
Dielectric substrate, the semisolid dielectric substrate includes porous PTFE plate, and the hole of the micropore of porous PTFE plate is 10nm-150nm,
The semimobile capillary colloid for mass transfer is filled with the micropore of porous PTFE plate.Wherein, capillary colloid includes ceramics
Grain, adsorbs nitric acid on ceramic particle, and the volume ratio of ceramic particle and nitric acid is 0.75, and the particle diameter of ceramic particle is 5nm-
30nm, the specific surface area of ceramic particle is about 1200 meters squared per grams.Nitric acid and ceramic particle are mixed into first and flowed with half
Property colloidal capillary colloid, then porous PTFE plate is allowed semi-fluid with being combined together with semimobile capillary colloid
The capillary colloid of dynamic property is fully filled with the micropore of the porous PTFE plate as support frame, and by making between Van der Waals force equimolecular
Firmly the support frame with porous PTFE plate is firmly combined as a whole.Hydrogen gas sensor response time 17s in the present embodiment,
Voltage is responded in more than 180mV, testing result is quick and precisely reliable.Under extreme conditions, 60 DEG C of high temperature, high humidity 90%RH, this
The hydrogen gas sensor response time in embodiment is less than 20s, and response voltage stills remain in more than 180mV, therefore still keeps
Effective state, can fast and accurately be detected.And before and after the hydrogen gas sensor progress vibrations experiment in the present embodiment
Performance test, the hydrogen gas sensor test performance after vibrations in the present embodiment is basically unchanged.
Embodiment 5：
Gas diffusion membrane 3 is made by gathering PVF.Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance be 100mm, the thickness of gas diffusion membrane 3 is 0.01mm, and the volume in storage oxygen space is 50ml.Dielectric substrate 21 is solid for half
State dielectric substrate, the semisolid dielectric substrate includes porous e-PTFE plates, and the hole of the micropore of porous e-PTFE plates is 1nm-
100nm, is filled with the semimobile capillary colloid for mass transfer in the micropore of porous e-PTFE plates.Wherein, capillary colloid
Including e-PTFE particles, phosphoric acid is adsorbed on e-PTFE particles, the volume ratio of e-PTFE particles and phosphoric acid is 0.1, e-PTFE
The particle diameter of grain is 1nm-10nm, and the specific surface area of e-PTFE particles is about 2000 meters squared per grams.First phosphoric acid and e-PTFE
Grain is mixed into the capillary colloid with semimobile colloidal, then porous e-PTFE plates with having semimobile capillary glue
Body is combined together, and allows semimobile capillary colloid to be fully filled with the micropore of the porous e-PTFE plates as support frame, and
Firmly it is combined as a whole by the support frame of Van der Waals force equimolecular intermolecular forces and porous e-PTFE plates.In the present embodiment
Hydrogen gas sensor response time 16s, response voltage in more than 180mV, testing result is quick and precisely reliable.In extreme condition
Under, 60 DEG C of high temperature, high humidity 90%RH, the hydrogen gas sensor response time in the present embodiment is less than 20s, and response voltage is remained in that
In more than 180mV, therefore effective state is still kept, can fast and accurately be detected.And the hydrogen in the present embodiment
Sensor carries out the performance test before and after vibrations experiment, and the hydrogen gas sensor test performance after vibrations in the present embodiment is basic
It is constant.
Embodiment 6：
Gas diffusion membrane 3 is made up of silicon rubber.Between the both sides relative with gas diffusion membrane 3 of working electrode 22 away from
It is 0.001mm from the thickness for 100mm, gas diffusion membrane 3, the volume in storage oxygen space is 100ml.Dielectric substrate 21 is semisolid
Dielectric substrate, the semisolid dielectric substrate includes porous ceramic plate, and the hole of the micropore of porous ceramic plate is 200nm-350nm,
The semimobile capillary colloid for mass transfer is filled with the micropore of porous ceramic plate.Wherein, capillary colloid includes dioxy
Silicon carbide particle, adsorbs sulfuric acid on silica dioxide granule, and the volume ratio of silica dioxide granule and sulfuric acid is 0.1, silica
The particle diameter of grain is 10nm-50nm, and the specific surface area of silica dioxide granule is about 1500 meters squared per grams.First sulfuric acid and dioxy
Silicon carbide particle is mixed into the capillary colloid with semimobile colloidal, then porous ceramic plate with having semimobile hair
Thin colloid is combined together, and allows semimobile capillary colloid to be fully filled with the micropore of the porous ceramic plate as support frame,
And be firmly combined as a whole by the support frame of Van der Waals force equimolecular intermolecular forces and porous ceramic plate.In the present embodiment
Hydrogen gas sensor response time 15s, response voltage in more than 180mV, testing result is quick and precisely reliable.In extreme condition
Under, 60 DEG C of high temperature, high humidity 90%RH, the hydrogen gas sensor response time in the present embodiment is less than 20s, and response voltage is remained in that
In more than 180mV, therefore effective state is still kept, can fast and accurately be detected.And the hydrogen in the present embodiment
Sensor carries out the performance test before and after vibrations experiment, and the hydrogen gas sensor test performance after vibrations in the present embodiment is basic
It is constant.
Embodiment 7：
Gas diffusion membrane 3 is made up of polytetrafluoroethylene (PTFE)-hexafluoropropylene copolymer.Working electrode 22 and gas diffusion membrane
The distance between 3 relative both sides are 0.01mm, and the thickness of gas diffusion membrane 3 is 0.01mm, and the volume in storage oxygen space is
0.1ml.Dielectric substrate 21 is semisolid dielectric substrate, and the semisolid dielectric substrate includes porous ceramic plate, porous ceramic plate
The hole of micropore is 350nm-1000nm, and the semimobile capillary glue for mass transfer is filled with the micropore of porous ceramic plate
Body.Wherein, capillary colloid includes silica dioxide granule, and sulfuric acid, silica dioxide granule and sulfuric acid are adsorbed on silica dioxide granule
Volume ratio be 0.1, the particle diameter of silica dioxide granule is 40nm-50nm, and the specific surface area of silica dioxide granule is about 300 squares
Rice/gram.Sulfuric acid and silica dioxide granule are mixed into the capillary colloid with semimobile colloidal first, then porous pottery
Porcelain plate allows semimobile capillary colloid to be fully filled with as support rib with being combined together with semimobile capillary colloid
The micropore of the porous ceramic plate of frame, and it is firm by the support frame of Van der Waals force equimolecular intermolecular forces and porous ceramic plate
It is combined as a whole.Hydrogen gas sensor response time 18s in the present embodiment, response voltage is in more than 180mV, and testing result is quick
Accurately and reliably.Under extreme conditions, the hydrogen gas sensor response time in 60 DEG C of high temperature, high humidity 90%RH, the present embodiment is less than
20s, response voltage stills remain in more than 180mV, therefore still keeps effective state, can fast and accurately be examined
Survey.And the hydrogen gas sensor in the present embodiment carries out the performance test before and after vibrations experiment, after vibrations in the present embodiment
Hydrogen gas sensor test performance is basically unchanged.
Embodiment 8：
Gas diffusion membrane 3 is made up of polyethylene-TFE copolymer.Working electrode 22 and the phase of gas diffusion membrane 3
To the distance between both sides be 2mm, the thickness of gas diffusion membrane 3 is 0.1mm, and the volume in storage oxygen space is 5ml.Dielectric substrate
21 be semisolid dielectric substrate, and the semisolid dielectric substrate includes porous ceramic plate, and the hole of the micropore of porous ceramic plate is
1000nm-10000nm, is filled with the semimobile capillary colloid for mass transfer in the micropore of porous ceramic plate.Wherein, hair
Thin colloid includes silica dioxide granule, adsorbs sulfuric acid on silica dioxide granule, and the volume ratio of silica dioxide granule and sulfuric acid is
0.3, the particle diameter of silica dioxide granule is 10nm-30nm, and the specific surface area of silica dioxide granule is about 1000 meters squared per grams.It is first
Sulfuric acid and silica dioxide granule are first mixed into the capillary colloid with semimobile colloidal, then porous ceramic plate and tool
There is semimobile capillary colloid to be combined together, allow semimobile capillary colloid to be fully filled with as the porous of support frame
The micropore of ceramic wafer, and firmly it is combined into one by the support frame of Van der Waals force equimolecular intermolecular forces and porous ceramic plate
Body.Hydrogen gas sensor response time 17s in the present embodiment, response voltage is in more than 180mV, and testing result quick and precisely may be used
Lean on.Under extreme conditions, the hydrogen gas sensor response time in 60 DEG C of high temperature, high humidity 90%RH, the present embodiment is less than 20s, rings
Answer voltage to still remain in more than 180mV, therefore still keep effective state, can fast and accurately be detected.And this
Hydrogen gas sensor in embodiment carries out the performance test before and after vibrations experiment, the hydrogen sensing after vibrations in the present embodiment
Device test performance is basically unchanged.
Embodiment 9：
Gas diffusion membrane 3 is made up of polytetrafluoroethylene (PTFE).Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance be 2mm, the thickness of gas diffusion membrane 3 is 0.1mm, and the volume in storage oxygen space is 5ml.Dielectric substrate 21 is semisolid electricity
Matter layer is solved, the semisolid dielectric substrate includes porous ceramic plate, and the hole of the micropore of porous ceramic plate is 30nm-120nm, many
The semimobile capillary colloid for mass transfer is filled with the micropore of hole ceramic wafer.Wherein, capillary colloid includes silica
Particle, adsorbs sulfuric acid on silica dioxide granule, and the volume ratio of silica dioxide granule and sulfuric acid is 1, the grain of silica dioxide granule
Footpath is 5nm-10nm, and the specific surface area of silica dioxide granule is about 1300 meters squared per grams.First sulfuric acid and silica dioxide granule
The capillary colloid with semimobile colloidal is mixed into, then porous ceramic plate with having semimobile capillary colloid knot
It is combined, allows semimobile capillary colloid to be fully filled with the micropore of the porous ceramic plate as support frame, and pass through model
The support frame of De Huali equimoleculars intermolecular forces and porous ceramic plate is firmly combined as a whole.Hydrogen in the present embodiment is passed
Sensor response time 18s, response voltage is in more than 180mV, and testing result is quick and precisely reliable.Under extreme conditions, high temperature 60
DEG C, high humidity 90%RH, the hydrogen gas sensor response time in the present embodiment is less than 20s, response voltage still remain in 180mV with
On, therefore effective state is still kept, can fast and accurately it be detected.And the hydrogen gas sensor in the present embodiment is carried out
Performance test before and after vibrations experiment, the hydrogen gas sensor test performance after vibrations in the present embodiment is basically unchanged.
Embodiment 10：
Gas diffusion membrane 3 is made up of polytetrafluoroethylene (PTFE).Between the both sides relative with gas diffusion membrane 3 of working electrode 22
Distance be 2mm, the thickness of gas diffusion membrane 3 is 0.1mm, and the volume in storage oxygen space is 5ml.Dielectric substrate 21 is semisolid electricity
Matter layer is solved, the semisolid dielectric substrate includes porous ceramic plate, and the hole of the micropore of porous ceramic plate is 30nm-120nm, many
The semimobile capillary colloid for mass transfer is filled with the micropore of hole ceramic wafer.Wherein, capillary colloid includes silica
Particle, adsorbs sulfuric acid on silica dioxide granule, and the volume ratio of silica dioxide granule and sulfuric acid is 1.2, silica dioxide granule
Particle diameter is 5nm-10nm, and the specific surface area of silica dioxide granule is about 1300 meters squared per grams.First sulfuric acid and silica
Grain is mixed into the capillary colloid with semimobile colloidal, then porous ceramic plate with having semimobile capillary colloid
It is combined together, allows semimobile capillary colloid to be fully filled with the micropore of the porous ceramic plate as support frame, and pass through
The support frame of Van der Waals force equimolecular intermolecular forces and porous ceramic plate is firmly combined as a whole.Hydrogen in the present embodiment
Sensor response time 16s, response voltage is in more than 180mV, and testing result is quick and precisely reliable.Under extreme conditions, high temperature
60 DEG C, high humidity 90%RH, the hydrogen gas sensor response time in the present embodiment is less than 20s, and response voltage stills remain in 180mV
More than, therefore effective state is still kept, can fast and accurately it be detected.And the hydrogen gas sensor in the present embodiment enters
Performance test before and after row vibrations experiment, the hydrogen gas sensor test performance after vibrations in the present embodiment is basically unchanged.
It should be appreciated that it will be understood by those skilled in the art that can according to the above description be improved or converted, but this
A little improvement or conversion should all belong within the protection domain of the utility model appended claims.
Claims (10)
1. a kind of hydrogen gas sensor for quick detection low-concentration hydrogen, including housing (1), are installed in the housing (1)
There is gas detection cell (2), the gas detection cell (2) includes dielectric substrate (21) and tied with the dielectric substrate (21)
Incorporated working electrode (22), to electrode (23) and reference electrode (24), it is characterised in that the interior direction of the housing (1)
The side of the working electrode (22) is provided with gas diffusion membrane (3), the gas diffusion membrane (3) and the working electrode (22)
Between seal to be formed by seal (4) and be used for the working electrode reaction gas that is reacted on the working electrode (22) of hydrogen
Room (5), the gas diffusion membrane (3) is the gas diffusion membrane of non-porous structure, and the dielectric substrate (21) is solid-state electrolyte layer
Or semisolid dielectric substrate.
2. hydrogen gas sensor according to claim 1, it is characterised in that the working electrode (22) and the gas diffusion
The distance between relative both sides of film (3) are 0.01mm-100mm.
3. hydrogen gas sensor according to claim 1, it is characterised in that the thickness of the gas diffusion membrane (3) is
0.001mm-0.1mm。
4. hydrogen gas sensor according to claim 1, it is characterised in that the gas diffusion membrane (3) is by polytetrafluoroethyl-ne
Alkene, gathered PVF, polytetrafluoroethylene (PTFE)-hexafluoropropylene copolymer, the vinyl ether copolymers of polytetrafluoroethylene (PTFE)-perfluor third, polyethylene-
What any one or a few mixture formed in TFE copolymer, polyimides, silicon rubber, fluorination silicon rubber was made
Gas diffusion membrane.
5. hydrogen gas sensor according to claim 1, it is characterised in that the housing (1) includes the main body with opening
(11) it is located on the lid (12) at the opening of the main body (11), the side wall of the lid (12) with lid and is provided with sealing ring
(13), the inwall at the opening of the housing (1) is formed with the recess (14) matched with the sealing ring (13).
6. hydrogen gas sensor according to claim 5, it is characterised in that the sealing ring (13) is by fluorubber or silicon rubber
The sealing ring that glue is made.
7. hydrogen gas sensor according to claim 1, it is characterised in that the seal (4) is gasket seal, described close
The thickness of gasket is 0.01-10mm.
8. hydrogen gas sensor according to claim 7, it is characterised in that the gasket seal is by fluorubber or silicon rubber
The gasket seal being made.
9. hydrogen gas sensor according to claim 1, it is characterised in that the working electrode (22) is located at the electrolyte
The side of layer (21), it is described to electrode (23) and reference electrode (24) positioned at the opposite side of the dielectric substrate (21) and described right
Electrode (23) and reference electrode (24) are set up in parallel in the opposite side of the dielectric substrate (21).
10. hydrogen gas sensor according to claim 9, it is characterised in that described to the formed below useful of electrode (23)
In the storage oxygen space (6) of storage oxygen, the volume of storage oxygen space (6) is 0.1-100ml.
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| CN201621457485.8U CN206470229U (en) | 2016-12-28 | 2016-12-28 | A kind of hydrogen gas sensor for quick detection low-concentration hydrogen |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108051032A (en) * | 2017-12-20 | 2018-05-18 | 国网新疆电力有限公司吐鲁番供电公司 | The on-line monitoring system of the few oily equipment of substation |
| CN108254420A (en) * | 2016-12-28 | 2018-07-06 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor for quickly detection low-concentration hydrogen |
| CN108318567A (en) * | 2018-04-18 | 2018-07-24 | 深圳市普晟传感技术有限公司 | A kind of formaldehyde gas sensor |
| CN108680617A (en) * | 2018-03-26 | 2018-10-19 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108254420A (en) * | 2016-12-28 | 2018-07-06 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor for quickly detection low-concentration hydrogen |
| CN108254420B (en) * | 2016-12-28 | 2024-03-12 | 深圳市普晟传感技术有限公司 | Hydrogen sensor for rapidly detecting low-concentration hydrogen |
| CN108051032A (en) * | 2017-12-20 | 2018-05-18 | 国网新疆电力有限公司吐鲁番供电公司 | The on-line monitoring system of the few oily equipment of substation |
| CN108680617A (en) * | 2018-03-26 | 2018-10-19 | 深圳市普晟传感技术有限公司 | A kind of hydrogen gas sensor |
| CN108680617B (en) * | 2018-03-26 | 2021-01-26 | 深圳市普晟传感技术有限公司 | Hydrogen sensor |
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