CN105958090A - Fuel cell realizing rapid detection of hydrogen leakage - Google Patents

Fuel cell realizing rapid detection of hydrogen leakage Download PDF

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Publication number
CN105958090A
CN105958090A CN201610259421.5A CN201610259421A CN105958090A CN 105958090 A CN105958090 A CN 105958090A CN 201610259421 A CN201610259421 A CN 201610259421A CN 105958090 A CN105958090 A CN 105958090A
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gas
air
sensitive
glass substrate
quartz glass
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林业城
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
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  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Analytical Chemistry (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

The invention relates to a fuel cell realizing rapid detection of hydrogen leakage. The fuel cell includes an anode chamber, a cathode chamber, a separation film, and a gasochromic gas sensor disposed inside of the fuel cell shell, and the anode chamber and the cathode chamber are separated by the separation film. The fuel in the anode chamber is glucose, and the fuel in the cathode chamber is oxygen. Microbes adhere to the surfaces of the cell anode connected with the anode chamber and the cell cathode connected with the cathode chamber extending to outside of the shell, and the microbes adhering to the anode belong to citrobacter. The cathode is prepared from a single layer stainless steel wire, and the gasochromic gas sensor comprises a sensitive unit, a heating unit, and a data reading unit. The heating unit and the data reading unit are connected with a tungsten oxide gas-sensitive film of the sensitive unit, the heating unit is used as a heating source of the tungsten oxide gas-sensitive film when the film works, and the sensitive unit is a double-layer structure with the hollow structure in the middle part.

Description

A kind of fuel cell realizing quickly detecting hydrogen leak
Technical field
The application relates to power domain, is specifically related to the fuel cell that can realize quickly detecting hydrogen leak.
Background technology
The fast development of microbiological fuel cell all brings great convenience to production and the life of people, not only protects Environment, and the development of beneficially economic technology.
But, the use of the fuel cell in correlation technique is more limited to, and is typically only and utilizes fuel cell to provide the energy, And the situation using the element of fuel cell to produce hydrogen can not be monitored in real time, when there is hydrogen gas leakage, need to install separately Equipment Inspection, wastes substantial amounts of man power and material and is not easy to monitoring.
Summary of the invention
For overcoming problem present in correlation technique, the application provides a kind of and realizes quickly detecting hydrogen leak Fuel cell.
First aspect according to the embodiment of the present application, it is provided that a kind of fuel cell realizing quickly detecting hydrogen leak, Including including anode chamber, cathode chamber, separation membrane and being arranged on the gas-discoloration gas sensor within fuel cell enclosure, described Anode chamber and cathode chamber are separated by separation membrane；Fuel in described anode chamber is glucose, and the fuel in described cathode chamber is Oxygen, the surface extending to the anode of the jointed anode room outside shell and the battery cathode of connection cathode chamber is all attached with micro- Biological；The described microorganism being attached to anode belongs to Citrobacter, and described negative electrode uses monolayer stainless (steel) wire to be prepared from； Described gas-discoloration gas sensor includes sensing unit, heating unit and data-reading unit；Described heating unit and data Read unit to be connected with the tungsten oxide air-sensitive film of sensing unit；When described heating unit works as tungsten oxide air-sensitive film Heating source；Data-reading unit processes the conductivity variations signal of tungsten oxide air-sensitive film to show the concentration value of object gas； Described sensing unit be middle part be the double-decker of hollow structure, form that double-deck A face structure is relative with B face structure puts Putting, distance 500 μm, the periphery of A face structure and the handing-over of B face structure uses colloid to seal；Described A face include quartz glass substrate, Interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive film layer is doping SnO2WO3Thin film, described B face includes quartz glass Substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nano wire film doping ZnTPP-2-NO2, in the structure of described B face It is additionally provided with 2 for air-vent that object gas penetrates.
Second aspect according to the embodiment of the present application, it is provided that a kind of fuel cell realizing quickly detecting hydrogen leak Preparation method, comprises the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
As preferably, in A face, SnO2Granularity less than 50nm, WO3Air-sensitive film layer thickness is 700nm；Air-sensitive is surveyed Examination completes on Testing system of gas-sensor built, puts in quartz ampoule by the device made, and heating unit heats makes sensing unit Operating temperature be 120 DEG C, after stable, be passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, then Secondary it is passed through pure air, records WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S =R (NO2)/R (air), response time be defined as being passed through resistance variations after test gas to maximum changes in resistance 80% needed for The time wanted；Test finds, this tungsten oxide air-sensitive film is at the NO of 8ppm concentration2Gas medium sensitivity is 30；During minimum response Between be 15s；Through 100 testing fatigues, electrical response value drops to original 86%；
As preferably, in B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer dense to difference Degree H2WO in atmosphere3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is certain for being passed through Concentration H2Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, relative light transmission with wavelength change, Minimum 4%, it is 59.7% to the maximum, through about 10min, relative light transmission tends towards stability, and thin film color is by original transparent change For blueness.
The technical scheme that embodiments herein provides can include following beneficial effect:
1. the application is using monolayer stainless (steel) wire to prepare negative electrode, and its power carries the microorganism combustion of activated carbon cathode than carbon cloth Material battery is low；Owing to the anode microorganism of the application belongs to Citrobacter, can the most stably produce electricity, show Excellent performance；Due to the WO in the application3Air-sensitive film has gas-discoloration character and air-sensitive character, therefore uses it to make Fuel cell can external power supply and heating in the case of measure NO2Concentration, meanwhile, is provided with conduct in this fuel cell The heating element heater of thermal source, therefore its can not heat with nonconducting in the case of, rely solely on the cosmetic variation of WO3 gas sensitive Hydrogen can be detected, show the hydrogen detection performance of excellence.
2. the sensing element employed in the fuel cell of the application is at configuration aspects, creative employing duplicature knot Structure, combines gas-sensitive property and the gas-discoloration characteristic of tungsten oxide material, increases the range of application of device；Tungsten oxide air-sensitive is thin Film is made by magnetically controlled sputter method based on Film-mode resistor sensor, thin film, by controlling partial pressure of oxygen and mixing in manufacturing process Miscellaneous stannum oxide so that thin film is to NO2Selectivity be all greatly improved with sensitivity；Tungsten oxide gas chromism film is that tungsten oxide is received Rice noodle doping tetraphenylporphyrin zinc derivative (ZnTPP-2-NO2) material, this dopant material, as catalyst, substantially increases oxygen Change tungsten nanowires to H2Reactivity, improve sensitivity, and achieve " smell-seeing " to hydrogen and measure.
Aspect and advantage that the application adds will part be given in the following description, and part will become from the following description Obtain substantially, or recognized by the practice of the application.It should be appreciated that above general description and details hereinafter only describe It is exemplary and explanatory, the application can not be limited.
Accompanying drawing explanation
Accompanying drawing herein is merged in description and constitutes the part of this specification, it is shown that meet the enforcement of the present invention Example, and for explaining the principle of the present invention together with description.
Fig. 1 is the schematic diagram of the sensor that the present invention uses.
Fig. 2 is the flow chart of the method preparing the sensor in Fig. 1.
Wherein: 1-quartz glass substrate, 2-interdigital electrode layer, 3-WO3Air-sensitive film layer, 4-hollow structure, 5-WO3Gas causes Photochromic layer.
Detailed description of the invention
Here will illustrate exemplary embodiment in detail, its example represents in the accompanying drawings.Explained below relates to During accompanying drawing, unless otherwise indicated, the same numbers in different accompanying drawings represents same or analogous key element.Following exemplary embodiment Described in embodiment do not represent all embodiments consistent with the present invention.On the contrary, they are only with the most appended The example of the apparatus and method that some aspects that described in detail in claims, the present invention are consistent.
Following disclosure provides many different embodiments or example for realizing the different structure of the application.For letter Changing disclosure herein, hereinafter parts and setting to specific examples are described.Certainly, they are the most merely illustrative, and It is not intended to limit the application.Additionally, the application can in different examples repeat reference numerals and/or letter.This heavy It is for purposes of simplicity and clarity again, itself is more than the relation between various embodiment being discussed and/or arranging.This Outward, the various specific technique that this application provides and the example of material, but those of ordinary skill in the art it can be appreciated that The applicability of other techniques and/or the use of other materials.It addition, fisrt feature described below Second Eigenvalue " on " Structure can include that the first and second features are formed as the embodiment directly contacted, it is also possible to include that other feature is formed at Embodiment between first and second features, such first and second features are not likely to be directly contact.
In the description of the present application, it should be noted that unless otherwise prescribed and limit, term " is installed ", " being connected ", " connect " and should be interpreted broadly, for example, it may be mechanically connected or electrical connection, it is also possible to be the connection of two element internals, can Being to be joined directly together, it is also possible to be indirectly connected to by intermediary, for the ordinary skill in the art, can basis Concrete condition understands the concrete meaning of above-mentioned term.
Modern society, along with economic and industry development, the consumption of various natural resourcess is continuously increased by the mankind, by In the shortcoming of pursuit economic goal with environmental consciousness, the pollution problem of environment is the most serious.Meanwhile, gas side is shown Face, the leakage of gas in various inflammable, explosive, the toxic gas discharged in productive life and environment, pollution are also people's wealth Produce safety to threaten greatly with the one of personal safety.Therefore, gas sensor technology is one of important topic of current research.Gas passes Sensor is a kind of can to change and the device effectively monitored or device, its foundation by perception surrounding target gas levels Be physical principle or chemical reaction etc., the type of gas sensor mainly has semiconductor gas sensor, electrochemical gas to pass Sensor, catalytic combustion type gas sensor, optical profile type gas sensor etc..WO3It is a kind of preferably controllable color change material, can be real Now visible ray and near-infrared radiation transmitance are continuously adjusted.Amorphous WO from Deb reported first in 19693Thin film electroluminescent Since discoloration effect, find the performance such as its gas-discoloration, photochromic, thermochromism successively, meanwhile, as transiting metal oxidation Thing, Tungstic anhydride. is to some gas, such as NO2、NO、NH3、H2、H2S etc. all show sensitivity characteristic；Compared with electrochromic device, WO3The advantages such as it is simple that gas-discoloration device has system structure, relative inexpensiveness, therefore by its gas-discoloration characteristic and air-sensitive Characteristic combines, the great significance to gas sensing optics type senser element.
Embodiment 1:
A kind of fuel cell realizing quickly detecting hydrogen leak, including including anode chamber, cathode chamber, separation membrane and setting Putting at the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber are separated by separation membrane；Institute Stating the fuel in anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to jointed anode room outside shell The surface of the battery cathode of anode and connection cathode chamber is all attached with microorganism；The described microorganism being attached to anode belongs to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from.
Fig. 1 is the schematic diagram of the gas-discoloration gas sensor that the present invention uses.With reference to Fig. 1, this sensor includes sensitivity Unit, heating unit and data-reading unit；The tungsten oxide air-sensitive of described heating unit and data-reading unit and sensing unit Thin film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Data-reading unit processes tungsten oxide The conductivity variations signal of air-sensitive film is to show the concentration value of object gas；Described sensing unit is hollow structure in the middle part of being Double-decker, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, and A face structure and B face structure are handed over The periphery connect uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive Thin layer is doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer For WO3Nano wire film doping ZnTPP-2-NO2(tetraphenylporphyrin zinc derivative), described B face structure is additionally provided with 2 use In the air-vent that object gas penetrates.
Fig. 2 is according to the flow chart preparing fuel cell shown in an exemplary embodiment, as in figure 2 it is shown, include following Step:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
As preferably, in A face, SnO2Granularity less than 50nm, WO3Air-sensitive film layer thickness is 700nm；Air-sensitive is surveyed Examination completes on Testing system of gas-sensor built, puts in quartz ampoule by the device made, and heating unit heats makes sensing unit Operating temperature be 120 DEG C, after stable, be passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, then Secondary it is passed through pure air, records WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S =R (NO2)/R (air), response time be defined as being passed through resistance variations after test gas to maximum changes in resistance 80% needed for The time wanted；Test finds, this tungsten oxide air-sensitive film is at the NO of 8ppm concentration2Gas medium sensitivity is 30；During minimum response Between be 15s；Through 100 testing fatigues, electrical response value drops to original 86%；
As preferably, in B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer dense to difference Degree H2WO in atmosphere3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is certain for being passed through Concentration H2Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, relative light transmission with wavelength change, Minimum 4%, it is 59.7% to the maximum, through about 10min, relative light transmission tends towards stability, and thin film color is by original transparent change For blueness.
About the device in above-described embodiment, wherein modules performs the concrete mode of operation in relevant the method Embodiment in be described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, SnO2Granularity less than 50nm, WO3Air-sensitive film layer thickness is 700nm；Air-sensitive is tested at gas sensor Completing in test system, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure sky Gas, records WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air) after, response time is defined as being passed through test gas resistance variations to maximum changes in resistance 80% required for time.Survey Examination finds, this tungsten oxide air-sensitive film is at the NO of 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 15s；Pass through 100 testing fatigues, electrical response value drops to original 86%.WO3When air-sensitive film shows good sensitivity, response Between and repeatability.
In B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2In atmosphere WO3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Up-to-date style The light transmittance of product, relative light transmission:, it is being passed through H2When concentration is 5000ppm, relative light transmission is with wavelength change, minimum 4%, it is 59.7% to the maximum, and through about 10min, relative light transmission tends towards stability, it is seen that be passed through with tested gas, tungsten oxide Gas-discoloration layer light transmittance declines, and shows as thin film color and transparent is become blue from original, and response time is short, shows good Gasochromic property.
The operation principle of the gas sensor used in the application is: gas sensor is important point of sensing technology ?.Can be divided into by gas sensor dissimilar according to structure and material etc., wherein, Metal Oxide Gas Sensors is used Sensitive prime material be broad stopband n-type metal oxide semiconductor, it all shows good sensitivity characteristic to multiple gases.Half The sensitive mechanism of conductor metal Oxide Gas Sensors is: sensitive material is made into the knot being beneficial to contact air into thin film etc. Structure, under heating state, when it is exposed in air, the total surface of sensitive material is to adsorb a certain amount of oxonium ion, shape Become surface potential barrier and space charge layer, the sheet electron concentration of sensitive material can be made to decline, and then electrical conductivity declines；When target gas (such as CO, H when body is reducibility gas2), this reducibility gas can adsorb on sensitive material surface, and occurs anti-with the oxygen on surface Should, make sheet electron concentration increase, electrical conductivity rises therewith；When object gas is oxidizing gas (such as NO2), this oxidisability The gas absorption on sensitive material surface further add the adsorbance of oxygen so that under the electrical conductivity of sensitive material is further Fall；The i.e. concentration of object gas and the electrical conductivity of sensitive material has dependency, thus, by measuring the change of sensitive material electrical conductivity Change thus measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes material, generation is right The colour developing effect that the light of wavelengths characteristic absorbs, the absorption spectrum of material can change, and macro manifestations is the change of material color. Specific to WO3After contact hydrogen, itself and hydrogen generation reversible reaction, tungsten bronze structure (H can be formedxWO4), owing to this structure is Blueness, shows as WO3The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring the determination of light transmittance hydrogen of thin film The concentration of gas.
The application is based on WO3The gas-discoloration character of material and air-sensitive character, be incorporated into by double membrane structure；One side Face, WO3Air-sensitive film can measure NO in the case of external power supply and heating2Concentration, on the other hand, can not heat and not Power up etc. in the environment of having particular/special requirement, WO3Air-sensitive thin film material shows limitation, now can pass through WO3Gas-discoloration is thin Film is to H2Detect.
Embodiment 2
A kind of fuel cell realizing quickly detecting hydrogen leak, including including anode chamber, cathode chamber, separation membrane and setting Putting at the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber are separated by separation membrane；Institute Stating the fuel in anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to jointed anode room outside shell The surface of the battery cathode of anode and connection cathode chamber is all attached with microorganism；The described microorganism being attached to anode belongs to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from.
Fig. 1 is the schematic diagram of the gas-discoloration gas sensor that the present invention uses.With reference to Fig. 1, this sensor includes sensitivity Unit, heating unit and data-reading unit；The tungsten oxide air-sensitive of described heating unit and data-reading unit and sensing unit Thin film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Data-reading unit processes tungsten oxide The conductivity variations signal of air-sensitive film is to show the concentration value of object gas；Described sensing unit is hollow structure in the middle part of being Double-decker, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, and A face structure and B face structure are handed over The periphery connect uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive Thin layer is doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer For WO3Nano wire film doping ZnTPP-2-NO2(tetraphenylporphyrin zinc derivative), described B face structure is additionally provided with 2 use In the air-vent that object gas penetrates.
Fig. 2 is according to the flow chart preparing fuel cell shown in an exemplary embodiment, as in figure 2 it is shown, include following Step:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
About the device in above-described embodiment, wherein modules performs the concrete mode of operation in relevant the method Embodiment in be described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, SnO2Granularity 45nm, WO3Air-sensitive film layer thickness is 600nm；Air-sensitive test is tested at gas sensor Completing in system, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air, note Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air) after, response time is defined as being passed through test gas resistance variations to maximum changes in resistance 80% required for time.Survey Examination finds, this tungsten oxide air-sensitive film is at the NO of 9ppm concentration2Gas medium sensitivity is 40；Best-case Response Time is 20s；Pass through 100 testing fatigues, electrical response value drops to original 84%.WO3When air-sensitive film shows good sensitivity, response Between and repeatability.
In B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2In atmosphere WO3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Up-to-date style The light transmittance of product, relative light transmission: T/T0, it is being passed through H2When concentration is 5500ppm, relative light transmission is with wavelength change, minimum 6%, it is 60.5% to the maximum, and through about 10min, relative light transmission tends towards stability, it is seen that be passed through with tested gas, tungsten oxide Gas-discoloration layer light transmittance declines, and shows as thin film color and transparent is become blue from original, and response time is short, shows good Gasochromic property.
The operation principle of the gas sensor used in the application is: gas sensor is important point of sensing technology ?.Can be divided into by gas sensor dissimilar according to structure and material etc., wherein, Metal Oxide Gas Sensors is used Sensitive prime material be broad stopband n-type metal oxide semiconductor, it all shows good sensitivity characteristic to multiple gases.Half The sensitive mechanism of conductor metal Oxide Gas Sensors is: sensitive material is made into the knot being beneficial to contact air into thin film etc. Structure, under heating state, when it is exposed in air, the total surface of sensitive material is to adsorb a certain amount of oxonium ion, shape Become surface potential barrier and space charge layer, the sheet electron concentration of sensitive material can be made to decline, and then electrical conductivity declines；When target gas (such as CO, H when body is reducibility gas2), this reducibility gas can adsorb on sensitive material surface, and occurs anti-with the oxygen on surface Should, make sheet electron concentration increase, electrical conductivity rises therewith；When object gas is oxidizing gas (such as NO2), this oxidisability The gas absorption on sensitive material surface further add the adsorbance of oxygen so that under the electrical conductivity of sensitive material is further Fall；The i.e. concentration of object gas and the electrical conductivity of sensitive material has dependency, thus, by measuring the change of sensitive material electrical conductivity Change thus measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes material, generation is right The colour developing effect that the light of wavelengths characteristic absorbs, the absorption spectrum of material can change, and macro manifestations is the change of material color. Specific to WO3After contact hydrogen, itself and hydrogen generation reversible reaction, tungsten bronze structure (H can be formedxWO4), owing to this structure is Blueness, shows as WO3The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring the determination of light transmittance hydrogen of thin film The concentration of gas.
The application is based on WO3The gas-discoloration character of material and air-sensitive character, be incorporated into by double membrane structure；One side Face, WO3Air-sensitive film can measure NO in the case of external power supply and heating2Concentration, on the other hand, can not heat and not Power up etc. in the environment of having particular/special requirement, WO3Air-sensitive thin film material shows limitation, now can pass through WO3Gas-discoloration is thin Film is to H2Detect.
Embodiment 3:
A kind of fuel cell realizing quickly detecting hydrogen leak, including including anode chamber, cathode chamber, separation membrane and setting Putting at the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber are separated by separation membrane；Institute Stating the fuel in anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to jointed anode room outside shell The surface of the battery cathode of anode and connection cathode chamber is all attached with microorganism；The described microorganism being attached to anode belongs to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from.With reference to Fig. 1, this sensor includes sensing unit, adds Hot cell and data-reading unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；It is thin that data-reading unit processes tungsten oxide air-sensitive The conductivity variations signal of film is to show the concentration value of object gas；Described sensing unit is the double-deck knot that middle part is hollow structure Structure, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, A face structure and the week of B face structure handing-over Limit uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive film layer For doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Receive Rice noodle film doping ZnTPP-2-NO2, described B face structure is additionally provided with 2 for air-vent that object gas penetrates.
Fig. 2 is according to the flow chart preparing fuel cell shown in an exemplary embodiment, as in figure 2 it is shown, include following Step:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
About the device in above-described embodiment, wherein modules performs the concrete mode of operation in relevant the method Embodiment in be described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, SnO2Granularity 40nm, WO3Air-sensitive film layer thickness is 500nm；Air-sensitive test is tested at gas sensor Completing in system, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air, note Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air) after, response time is defined as being passed through test gas resistance variations to maximum changes in resistance 80% required for time.Survey Examination finds, this tungsten oxide air-sensitive film is at the NO of 10ppm concentration2Gas medium sensitivity is 50；Best-case Response Time is 30s；Warp Crossing 100 testing fatigues, electrical response value drops to original 80%.WO3Air-sensitive film shows good sensitivity, response Time and repeatability.
In B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2In atmosphere WO3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Up-to-date style The light transmittance of product, relative light transmission: T/T0, it is being passed through H2When concentration is 6000ppm, relative light transmission is with wavelength change, minimum 8%, it is 63.5% to the maximum, and through about 10min, relative light transmission tends towards stability, it is seen that be passed through with tested gas, tungsten oxide Gas-discoloration layer light transmittance declines, and shows as thin film color and transparent is become blue from original, and response time is short, shows good Gasochromic property.
The operation principle of the gas sensor used in the application is: gas sensor is important point of sensing technology ?.Can be divided into by gas sensor dissimilar according to structure and material etc., wherein, Metal Oxide Gas Sensors is used Sensitive prime material be broad stopband n-type metal oxide semiconductor, it all shows good sensitivity characteristic to multiple gases.Half The sensitive mechanism of conductor metal Oxide Gas Sensors is: sensitive material is made into the knot being beneficial to contact air into thin film etc. Structure, under heating state, when it is exposed in air, the total surface of sensitive material is to adsorb a certain amount of oxonium ion, shape Become surface potential barrier and space charge layer, the sheet electron concentration of sensitive material can be made to decline, and then electrical conductivity declines；When target gas (such as CO, H when body is reducibility gas2), this reducibility gas can adsorb on sensitive material surface, and occurs anti-with the oxygen on surface Should, make sheet electron concentration increase, electrical conductivity rises therewith；When object gas is oxidizing gas (such as NO2), this oxidisability The gas absorption on sensitive material surface further add the adsorbance of oxygen so that under the electrical conductivity of sensitive material is further Fall；The i.e. concentration of object gas and the electrical conductivity of sensitive material has dependency, thus, by measuring the change of sensitive material electrical conductivity Change thus measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes material, generation is right The colour developing effect that the light of wavelengths characteristic absorbs, the absorption spectrum of material can change, and macro manifestations is the change of material color. Specific to WO3After contact hydrogen, itself and hydrogen generation reversible reaction, tungsten bronze structure (H can be formedxWO4), owing to this structure is Blueness, shows as WO3The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring the determination of light transmittance hydrogen of thin film The concentration of gas.
The application is based on WO3The gas-discoloration character of material and air-sensitive character, be incorporated into by double membrane structure；One side Face, WO3Air-sensitive film can measure NO in the case of external power supply and heating2Concentration, on the other hand, can not heat and not Power up etc. in the environment of having particular/special requirement, WO3Air-sensitive thin film material shows limitation, now can pass through WO3Gas-discoloration is thin Film is to H2Detect.
Embodiment 4
A kind of fuel cell realizing quickly detecting hydrogen leak, including including anode chamber, cathode chamber, separation membrane and setting Putting at the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber are separated by separation membrane；Institute Stating the fuel in anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to jointed anode room outside shell The surface of the battery cathode of anode and connection cathode chamber is all attached with microorganism；The described microorganism being attached to anode belongs to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from.
Fig. 1 is the schematic diagram of the gas-discoloration gas sensor that the present invention uses.With reference to Fig. 1, this sensor includes sensitivity Unit, heating unit and data-reading unit；The tungsten oxide air-sensitive of described heating unit and data-reading unit and sensing unit Thin film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Data-reading unit processes tungsten oxide The conductivity variations signal of air-sensitive film is to show the concentration value of object gas；Described sensing unit is hollow structure in the middle part of being Double-decker, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, and A face structure and B face structure are handed over The periphery connect uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive Thin layer is doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer For WO3Nano wire film doping ZnTPP-2-NO2(tetraphenylporphyrin zinc derivative), described B face structure is additionally provided with 2 use In the air-vent that object gas penetrates.
Fig. 2 is according to the flow chart preparing fuel cell shown in an exemplary embodiment, as in figure 2 it is shown, include following Step:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
About the device in above-described embodiment, wherein modules performs the concrete mode of operation in relevant the method Embodiment in be described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, SnO2Granularity less than 30nm, WO3Air-sensitive film layer thickness is 400nm；Air-sensitive is tested at gas sensor Completing in test system, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure sky Gas, records WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air) after, response time is defined as being passed through test gas resistance variations to maximum changes in resistance 80% required for time.Survey Examination finds, this tungsten oxide air-sensitive film is at the NO of 15ppm concentration2Gas medium sensitivity is 65；Best-case Response Time is 35s；Warp Crossing 100 testing fatigues, electrical response value drops to original 80%.WO3Air-sensitive film shows good sensitivity, response Time and repeatability.
In B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2In atmosphere WO3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Up-to-date style The light transmittance of product, relative light transmission:, it is being passed through H2When concentration is 5500ppm, relative light transmission is with wavelength change, minimum 3.5%, it is 58.6% to the maximum, and through about 10min, relative light transmission tends towards stability, it is seen that be passed through with tested gas, oxidation Tungsten gas-discoloration layer light transmittance declines, and shows as thin film color and transparent is become blue from original, and response time is short, and performance is good Gasochromic property.
The operation principle of the gas sensor used in the application is: gas sensor is important point of sensing technology ?.Can be divided into by gas sensor dissimilar according to structure and material etc., wherein, Metal Oxide Gas Sensors is used Sensitive prime material be broad stopband n-type metal oxide semiconductor, it all shows good sensitivity characteristic to multiple gases.Half The sensitive mechanism of conductor metal Oxide Gas Sensors is: sensitive material is made into the knot being beneficial to contact air into thin film etc. Structure, under heating state, when it is exposed in air, the total surface of sensitive material is to adsorb a certain amount of oxonium ion, shape Become surface potential barrier and space charge layer, the sheet electron concentration of sensitive material can be made to decline, and then electrical conductivity declines；When target gas (such as CO, H when body is reducibility gas2), this reducibility gas can adsorb on sensitive material surface, and occurs anti-with the oxygen on surface Should, make sheet electron concentration increase, electrical conductivity rises therewith；When object gas is oxidizing gas (such as NO2), this oxidisability The gas absorption on sensitive material surface further add the adsorbance of oxygen so that under the electrical conductivity of sensitive material is further Fall；The i.e. concentration of object gas and the electrical conductivity of sensitive material has dependency, thus, by measuring the change of sensitive material electrical conductivity Change thus measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes material, generation is right The colour developing effect that the light of wavelengths characteristic absorbs, the absorption spectrum of material can change, and macro manifestations is the change of material color. Specific to WO3After contact hydrogen, itself and hydrogen generation reversible reaction, tungsten bronze structure (H can be formedxWO4), owing to this structure is Blueness, shows as WO3The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring the determination of light transmittance hydrogen of thin film The concentration of gas.
The application is based on WO3The gas-discoloration character of material and air-sensitive character, be incorporated into by double membrane structure；One side Face, WO3Air-sensitive film can measure NO in the case of external power supply and heating2Concentration, on the other hand, can not heat and not Power up etc. in the environment of having particular/special requirement, WO3Air-sensitive thin film material shows limitation, now can pass through WO3Gas-discoloration is thin Film is to H2Detect.
Embodiment 5
A kind of fuel cell realizing quickly detecting hydrogen leak, including including anode chamber, cathode chamber, separation membrane and setting Putting at the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber are separated by separation membrane；Institute Stating the fuel in anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to jointed anode room outside shell The surface of the battery cathode of anode and connection cathode chamber is all attached with microorganism；The described microorganism being attached to anode belongs to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from.
Fig. 1 is the schematic diagram of the gas-discoloration gas sensor that the present invention uses.With reference to Fig. 1, this sensor includes sensitivity Unit, heating unit and data-reading unit；The tungsten oxide air-sensitive of described heating unit and data-reading unit and sensing unit Thin film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Data-reading unit processes tungsten oxide The conductivity variations signal of air-sensitive film is to show the concentration value of object gas；Described sensing unit is hollow structure in the middle part of being Double-decker, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, and A face structure and B face structure are handed over The periphery connect uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3Air-sensitive Thin layer is doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer For WO3Nano wire film doping ZnTPP-2-NO2(tetraphenylporphyrin zinc derivative), described B face structure is additionally provided with 2 use In the air-vent that object gas penetrates.
Fig. 2 is according to the flow chart preparing fuel cell shown in an exemplary embodiment, as in figure 2 it is shown, include following Step:
S1, preparation A face structure, including following enforcement step: (1) takes the quartz glass substrate of certain size (4cm × 4cm) The end, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) spin coating one layer photoetching glue in quartz glass substrate, Thickness 1 μm, exposes 6s under interdigital electrode mask covers, and cleans with deionized water, use magnetic control after being then passed through development 50s Cr film thick for sputtering method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；(3) quartz glass substrate is put Enter in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, Operating pressure is 2.4Pa, and at the metal W target magnetic control sputtering 28min that target is purity 99.96%, target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes the quartz glass substrate of same size (4cm × 4cm) The end, sequentially passing through acetone, ethanol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate is dissolved in 200ml water, and the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then uses deionized water Cleaning until can't detect chloride ion, then active tungstic acid precipitation being dissolved in hydrogen peroxide, preparing colloidal sol, be spun on quartz glass In glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionization Water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, is heated to 150 DEG C of holdings in an oven 10h, then takes out quartz glass substrate and spends ionized water cleaning；(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2- NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode, made solution drop coating is existed Quartz glass substrate surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate in vacuum Drying baker is dried at 60 DEG C 12h, obtains the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation sun containing glucose Pole electrolyte and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install and separate Film also adds electrolyte such as anode chamber and cathode chamber, is fixedly arranged in battery case by the sensing element formed via step S1 and S2.
As preferably, the porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
About the device in above-described embodiment, wherein modules performs the concrete mode of operation in relevant the method Embodiment in be described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, SnO2Granularity less than 20nm, WO3Air-sensitive film layer thickness is 300nm；Air-sensitive is tested at gas sensor Completing in test system, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure sky Gas, records WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air) after, response time is defined as being passed through test gas resistance variations to maximum changes in resistance 80% required for time.Survey Examination finds, this tungsten oxide air-sensitive film is at the NO of 18ppm concentration2Gas medium sensitivity is 70；Best-case Response Time is 37s；Warp Crossing 100 testing fatigues, electrical response value drops to original 80.5%.WO3Air-sensitive film shows good sensitivity, sound Between Ying Shi and repeatability.
In B face, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2In atmosphere WO3Gas-discoloration layer carries out light transmittance test, defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Up-to-date style The light transmittance of product, relative light transmission:, it is being passed through H2When concentration is 6500ppm, relative light transmission is with wavelength change, minimum 2.5%, it is 60.5% to the maximum, and through about 10min, relative light transmission tends towards stability, it is seen that be passed through with tested gas, oxidation Tungsten gas-discoloration layer light transmittance declines, and shows as thin film color and transparent is become blue from original, and response time is short, and performance is good Gasochromic property.
The operation principle of the gas sensor used in the application is: gas sensor is important point of sensing technology ?.Can be divided into by gas sensor dissimilar according to structure and material etc., wherein, Metal Oxide Gas Sensors is used Sensitive prime material be broad stopband n-type metal oxide semiconductor, it all shows good sensitivity characteristic to multiple gases.Half The sensitive mechanism of conductor metal Oxide Gas Sensors is: sensitive material is made into the knot being beneficial to contact air into thin film etc. Structure, under heating state, when it is exposed in air, the total surface of sensitive material is to adsorb a certain amount of oxonium ion, shape Become surface potential barrier and space charge layer, the sheet electron concentration of sensitive material can be made to decline, and then electrical conductivity declines；When target gas (such as CO, H when body is reducibility gas2), this reducibility gas can adsorb on sensitive material surface, and occurs anti-with the oxygen on surface Should, make sheet electron concentration increase, electrical conductivity rises therewith；When object gas is oxidizing gas (such as NO2), this oxidisability The gas absorption on sensitive material surface further add the adsorbance of oxygen so that under the electrical conductivity of sensitive material is further Fall；The i.e. concentration of object gas and the electrical conductivity of sensitive material has dependency, thus, by measuring the change of sensitive material electrical conductivity Change thus measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes material, generation is right The colour developing effect that the light of wavelengths characteristic absorbs, the absorption spectrum of material can change, and macro manifestations is the change of material color. Specific to WO3After contact hydrogen, itself and hydrogen generation reversible reaction, tungsten bronze structure (H can be formedxWO4), owing to this structure is Blueness, shows as WO3The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring the determination of light transmittance hydrogen of thin film The concentration of gas.
Those skilled in the art, after considering description and putting into practice invention disclosed herein, will readily occur to its of the present invention Its embodiment.The application is intended to any modification, purposes or the adaptations of the present invention, these modification, purposes or Person's adaptations is followed the general principle of the present invention and includes the undocumented common knowledge in the art of the application Or conventional techniques means.Description and embodiments is considered only as exemplary, and true scope and spirit of the invention are by following Claim is pointed out.
It should be appreciated that the invention is not limited in precision architecture described above and illustrated in the accompanying drawings, and And various modifications and changes can carried out without departing from the scope.The scope of the present invention is only limited by appended claim.

Claims (5)

1. the fuel cell that can realize quickly detecting hydrogen leak, it is characterised in that: described fuel cell include anode chamber, Cathode chamber, separation membrane and be arranged on the gas-discoloration gas sensor within fuel cell enclosure, described anode chamber and cathode chamber Separated by separation membrane；Fuel in described anode chamber is glucose, and the fuel in described cathode chamber is oxygen, extends to shell The surface of the battery cathode of the anode of outer jointed anode room and connection cathode chamber is all attached with microorganism；It is attached to anode Described microorganism belong to Citrobacter, described negative electrode uses monolayer stainless (steel) wire to be prepared from；Described gas-discoloration gas Body sensor includes sensing unit, heating unit and data-reading unit；Described heating unit and data-reading unit are with sensitive The tungsten oxide air-sensitive film of unit connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Data are read Take the conductivity variations signal of cell processing tungsten oxide air-sensitive film to show the concentration value of object gas；Described sensing unit is Middle part is the double-decker of hollow structure, forms double-deck A face structure and B face structure is staggered relatively, distance 500 μm, A face The periphery of structure and the handing-over of B face structure uses colloid to seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Gas Sensitive film layer, WO3Air-sensitive film layer is doping SnO2WO3Thin film, described B face includes quartz glass substrate and WO3Gas-discoloration Layer, WO3Gas-discoloration layer is WO3Nano wire film doping ZnTPP-2-NO2, described B face structure is additionally provided with 2 for mesh The air-vent that gas body penetrates.
2. the preparation a kind of fuel cell realizing quickly detecting hydrogen leak described in claim 1, it is characterised in that include Following steps:
S1, preparation A face structure, including following enforcement step:
(1) take the quartz glass substrate of certain size (4cm × 4cm), sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；
(2) spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers, expose 6s, so After clean with deionized water after development 50s, use magnetically controlled sputter method to plate Cr film thick for one layer of 300nm as interdigital electrode Layer, then removes photoresist；
(3) quartz glass substrate is put in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Gaseous mixture Body, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, at the metal W target magnetic control sputtering that target is purity 99.96% 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, obtains the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film Layer；
S2, preparation B face structure, including following enforcement step:
(1) take the quartz glass substrate of same size (4cm × 4cm), sequentially pass through acetone, ethanol, deionized water, NaOH water-soluble Liquid, deionized water ultrasonic cleaning, the time is 20min；
(2) taking 20g sodium tungstate to be dissolved in 200ml water, the concentrated hydrochloric acid adding excess obtains active tungstic acid precipitation, is filtered, then Cleaning until can't detect chloride ion with deionized water, then active tungstic acid precipitation being dissolved in hydrogen peroxide, prepare colloidal sol, rotation Being applied in quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；
(3) taking sodium tungstate powder 4.12g and be dissolved in 60ml deionized water, regulating its pH with 3M HCl solution is 2.0, is subsequently adding Quartz glass substrate, as controlling agent, is lain in deionized water by 2.1g (0.3M) ammonium sulfate, after stirring 1 hour, pours into not In rust steel hydrothermal reaction kettle, being heated to 150 DEG C in an oven and keep 10h, then taking out quartz glass substrate, to spend ionized water clear Wash；
(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2-NO2It is configured to the solution of 5.0mg/ml, supersound process 20min, makes solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set spin speed as 3400rpm, spin-coating time is 70s, quartz glass substrate is finally dried at 60 DEG C in vacuum drying oven 12h, is adulterated ZnTPP-2-NO2WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, prepare electrode and electrolyte: it is standby that acid solution cleans the etched afterflush of stainless (steel) wire；The preparation anode electricity containing glucose Solve liquid and oxygenous catholyte；
S4, assembling: the stainless (steel) wire electrode made via step S3 is respectively charged into anode chamber and cathode chamber, install separation membrane also Add electrolyte such as anode chamber and cathode chamber, the sensing element formed via step S1 and S2 is fixedly arranged in battery case.
A kind of fuel cell realizing quickly detecting hydrogen leak the most according to claim 1 and 2, it is characterised in that: The porosity of=90% of described monolayer stainless (steel) wire, its aperture size is 100～150 μm.
A kind of fuel cell realizing quickly detecting hydrogen leak the most according to claim 2, it is characterised in that: A face In, SnO2Granularity less than 50nm, WO3Air-sensitive film layer thickness is 700nm；Air-sensitive is tested on Testing system of gas-sensor built Completing, put in quartz ampoule by the device made, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, treats steady After Ding, it is passed through by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air, records WO3Gas The resistance value of sensitive film layer, respectively R (NO2) and R (air), definition Gas-sensing measurment is: S=R (NO2)/R (air), response Timing definition be passed through test gas after resistance variations to maximum changes in resistance 80% required for time；Test finds, should Tungsten oxide air-sensitive film is at the NO of 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100 fatigues Test, electrical response value drops to original 86%.
A kind of fuel cell realizing quickly detecting hydrogen leak the most according to claim 2, it is characterised in that: B face In, WO3Nanowire length about 1 μm, diameter about 60nm；Use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer Carry out light transmittance test, define T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2Time sample light transmittance, phase To light transmittance:, it is being passed through H2When concentration is 5000ppm, relative light transmission with wavelength change, minimum 4%, be to the maximum 59.7%, through about 10min, relative light transmission tends towards stability, and thin film color transparent is become blue from original.
CN201610259421.5A 2016-04-21 2016-04-21 Fuel cell realizing rapid detection of hydrogen leakage Pending CN105958090A (en)

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