CN105513811A - Camping tent with high-repetitiveness gas detection function - Google Patents
Camping tent with high-repetitiveness gas detection function Download PDFInfo
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- CN105513811A CN105513811A CN201610021655.6A CN201610021655A CN105513811A CN 105513811 A CN105513811 A CN 105513811A CN 201610021655 A CN201610021655 A CN 201610021655A CN 105513811 A CN105513811 A CN 105513811A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a camping tent with a high-repetitiveness gas detection function. A detection device is arranged at the outer surface of the camping tent, is based on a self-energy supply sensing element, and comprises a data reading module and a gas identifying module; the self-energy supply sensing element comprises a dye sensitization solar cell module and a gas sensor module, and the dye sensitization solar cell module is used as a working power source of the gas sensor module to realize the self-energy supply effect. The camping tent has the advantages that when the camping tent is used outdoors, the harmful gases in the working environment of the camping tent can be quickly detected; the sensitivity is high, and the repetitiveness is high.
Description
Technical field
The present invention relates to tent field, more specifically relate to a kind of Camp tent with high duplication gas detect.
Background technology
Camp tent refers to the tent that can encamp out of doors, usually has function that is rainproof, sun-proof, that leak informaton, breathe freely and be incubated, considers different purposes, design different styles.
But, because the range of application of existing Camp tent is comparatively extensive, when it is in different operating environment, to which proposing new requirement functionally, such as to the measuring ability of hazardous gas.
Summary of the invention
The object of the invention is to avoid weak point of the prior art and a kind of Camp tent with high duplication gas detect is provided.
Object of the present invention is achieved through the following technical solutions:
Have a Camp tent for high duplication gas detect, the outer surface installation detecting device of this Camp tent, described checkout gear is based on self energizing sensing element, and this self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Dye sensitization of solar module can as the working power of gas sensor module, self-energizing effect is produced to it, when Camp tent uses out of doors, the fast detecting to pernicious gas in environment for use residing for it can be realized, highly sensitive, and repeatability is high, reaches the object of efficiency utilization solar energy simultaneously.
Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter 150nm of particle, the described length to carbon nano-tube on electrode is 15 μm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film as the composite sensitive material detecting gas together with porous silicon, and the aperture of described porous silicon is 30 ~ 70nm; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 300nm, and the thickness of described Ni film is 15nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 1:3 and the mixed liquor of deionized water, and corrosion current is 45mA/cm
2, etching time is 1h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 100nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Usefulness of the present invention is:
(1) the present invention is based on DSSC technology and gas sensor technology, design self-energizing gas sensor, namely the energy of working sensor is provided with DSSC; DSSC is connected with porous silicon-base gas sensor, comprises solar module, sensor assembly, data read module and gas detection module; Solar cell is used as the working power of transducer by solar power generation, produce self-energizing effect to gas sensor, and maximum using solar energy resources, decreases energy waste and environmental pollution.
(2) in DSSC in electrode, usually adopt Pt as to electrode catalyst agent material, but platinum is a kind of noble metal, expensive, the present invention adopts carbon nano-tube to substitute Pt as catalyst, makes simple, catalytic efficiency is high, cheap; Preparation cost reduces greatly, is conducive to wideling popularize application; In addition, in the present invention, gas sensor module adopts porous silicon to be sensitive material, simultaneously at porous silicon surface evaporation tungsten oxide layer film, porous silica material and tungsten oxide material are combined as composite sensitive material, in the quick environment-identification of energy, the situation of change of gas, highly sensitive, convenient and swift.
(3) the present invention is provided with the gas identification module that can identify gas type after data read module, the instruction support powder used in the gas detect component arranged in this module judges gas type fast, its work does not need dye sensitization solar cell module to provide energy when running, overall province has saved the energy, and achieves passive detection emission gases; Efficient and convenient.
Accompanying drawing explanation
Utilize accompanying drawing to be described further invention, but the embodiment in accompanying drawing does not form any limitation of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the following drawings.
Fig. 1 is the schematic diagram of Camp tent of the present invention.
Fig. 2 is the structural representation of dye sensitization solar cell module of the present invention.
Fig. 3 is gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of gas sensor module of the present invention.
Fig. 5 be dye sensitization solar cell module of the present invention and gas sensor module in conjunction with schematic diagram.
Fig. 6 is the structural representation of gas identification module of the present invention.
Embodiment
In general, after the gas component of senser in gas sensor in extraneous test environment changes, its physical quantity measured accordingly also can change, the specific gas componant changed detects by gas sensor, and then transformed the change of the signal of telecommunication of reflection gas componant change, such as resistance, electric capacity, dielectric etc.
Porous silicon is a kind of material with open structure, and it can by monocrystalline silicon or polysilicon be oxidized in hydrofluoric acid obtains.Porous silicon has the advantage such as good optical property, huge surface area, and at present, porous silicon is to humidity, organic gas, NO
x, CO
x, O
2, HCl etc. shows detection.Take porous silicon as the gas sensor of sensitive material, after mainly utilizing its adsorbed gas, the change of conductivity is to detect gas.When porous silicon is placed in detected gas environment, gas can in porous silicon surface generation suction-operated, gas molecule can capture hole or electronics from porous silicon surface, cause the resistance of porous silicon to change, namely can be recorded the change of gas concentration to be measured by the change of measuring porous silicon resistance or conductance.
There is following technical problem in the gas sensor in current correlation technique: at gas sensor operationally, need external power supply or battery to drive its work, a large amount of use battery can cause environmental pollution and energy waste, to environment, there is potential harm, therefore, the new gas transducer seeking a kind of environmental protection and energy saving is needed.Solar energy, as the continuable novel energy of one, is the basis of human survival and development.In future, solar power generation will become the main energy sources form of human society.At present, solar cell is mainly with silicon solar cell, DSSC and organic solar batteries form, wherein, the silicon solar cell of major part to be monocrystalline and polysilicon be representative on market, although it has, transformation efficiency is high, the advantage of stable performance, but when preparing silicon solar cell, refining high-purity silicon material needs the at substantial energy.
Under solar light irradiation, dye molecule absorbs luminous energy, and it is excited to excitation state by eigenstate, and due to the instability of excitation state, its excitation state electrons is transferred to from dye molecule the conductive layer that Nanometer Semiconductor Films passes through light anode, and then to external circuit; The dye molecule losing electronics can by I in the electrolyte that is close to
-revert to eigenstate, and I
-ion is oxidized to I
3-, electronics is transferred to electrode from external circuit, under the effect of catalyst, by I in electrolyte
3-be reduced to I
-, so circulate.
Based on this, the operation principle of device of the present invention is: DSSC is connected with gas sensor, data read module.Under solar radiation, in DSSC, dye molecule absorbs luminous energy, is excited, the electronics of release flows to external circuit through light anode, forms loop, to electrode by porous silicon-base gas sensor, data detection module, through the catalytic action of carbon nano-tube, go back I in original electrolyte
3-ion, so forms duty cycle; For gas sensor, under detected gas environment, porous silicon and tungsten oxide meeting adsorption gas molecule, its conductivity is caused to change, and then act on the change of electric current, now data monitoring module can detect change, finally shows this gas concentration in real time.
The invention provides a kind of Camp tent with high duplication gas detect, the outer surface installation detecting device of this Camp tent, described checkout gear is based on self energizing sensing element, and this self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Dye sensitization of solar module can as the working power of gas sensor module, self-energizing effect is produced to it, when Camp tent uses out of doors, the fast detecting to pernicious gas in environment for use residing for it can be realized, highly sensitive, and repeatability is high, reaches the object of efficiency utilization solar energy simultaneously.
In conjunction with legend the present invention made and further illustrating:
Fig. 1 is Camp tent schematic diagram of the present invention.Checkout gear 2 is installed on the outer surface of Camp tent 1.
Fig. 2 is the structural representation of dye sensitization solar cell module of the present invention.
Fig. 3 is gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of gas sensor module of the present invention.
Fig. 5 be dye sensitization solar cell module of the present invention and gas sensor module in conjunction with schematic diagram.
Fig. 6 is the structural representation of gas identification module of the present invention.
Wherein: the 10-stainless steel-based end, 11-silicon chip substrate, 12-silicon chip substrate, 13-dye sensitization solar cell module, 20-conductive catalytic layer, 21-Porous Silicon area, 23-gas sensor module, 30-electrolyte, 31-Au electrode, 32-tungsten oxide nano, 33-data read module, the substrate of 40-ITO electro-conductive glass, 43-framework, 50-to carbon nano-tube on electrode, 53-air admission hole, 60-TiO
2particle layer and dye molecules, 70-gas identification module, 71-shell body, 72-gas detect component, 73-diffusion control rete, 74-indicates support powder, 75-glass tube.
The invention will be further described with the following Examples.
Embodiment 1
A kind of Camp tent with high duplication gas detect that embodiments of the invention provide, the outer surface installation detecting device of this Camp tent, described checkout gear based on self energizing sensing element, and comprises data read module and gas identification module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter of particle is about 150nm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, and the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film together with porous silicon as the composite sensitive material detecting gas; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 500nm, and the thickness of described Ni film is 10nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 1:3 and the mixed liquor of deionized water, and corrosion current is 45mA/cm
2, etching time is 1h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 100nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Test data:
In obtained device, DSSC 15 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 30 ~ 70nm in gas sensor; During test, this device is put into 1m
3light tight hermetical testing container, get 100mW/cm
2xenon source simulated solar irradiation, respectively to the NO passing into variable concentrations in test container
2gas.
The sensitivity of gas represents with following formula: R%=(I
0± I
t/ I
0) × 100%, in formula, when light source power is constant, I
0for not passing into NO
2time device in size of current, I
tfor passing into NO
2size of current during test gas in device.
Test obtains, the optimum transformation efficiency about 11.6% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 9.3%, reproducible; When gas sensor working temperature about 40 DEG C, it is all put up the best performance to the selectivity of gas and sensitivity, wherein, to NO
2the detection limit of gas is 5ppm, to the NO of 100ppm
2, sensitivity is 72, response time 7s; To NH
3the detection limit of gas is 5ppm, to the NH of 100ppm
3, sensitivity reaches 56, response time 4s.
Embodiment 2:
A kind of Camp tent with high duplication gas detect that embodiments of the invention provide, the outer surface installation detecting device of this Camp tent, described checkout gear based on self energizing sensing element, and comprises data read module and gas identification module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter of particle is about 110nm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, and the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film together with porous silicon as the composite sensitive material detecting gas; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 300nm, and the thickness of described Ni film is 7nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 30 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 2:3 and the mixed liquor of deionized water, and corrosion current is 40mA/cm
2, etching time is 2h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 60nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Test data:
In obtained device, DSSC 7 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 5 ~ 25nm in gas sensor; During test, this device is put into 1m
3light tight hermetical testing container, get 100mW/cm
2xenon source simulated solar irradiation, respectively to the NO passing into variable concentrations in test container
2gas.
The sensitivity of gas represents with following formula: R%=(I
0± I
t/ I
0) × 100%, in formula, when light source power is constant, I
0for not passing into NO
2time device in size of current, I
tfor passing into NO
2size of current during test gas in device.
Test obtains, the optimum transformation efficiency about 9.5% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 7.4%, reproducible; When gas sensor working temperature about 40 DEG C, it is all put up the best performance to the selectivity of gas and sensitivity, wherein, to NO
2the detection limit of gas is 12ppm, to the NO of 100ppm
2, sensitivity is 52, response time 9s; To NH
3the detection limit of gas is 9ppm, to the NH of 100ppm
3, sensitivity reaches 50, response time 6s.
Embodiment 3
A kind of Camp tent with high duplication gas detect that embodiments of the invention provide, the outer surface installation detecting device of this Camp tent, described checkout gear based on self energizing sensing element, and comprises data read module and gas identification module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter of particle is about 120nm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, and the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film together with porous silicon as the composite sensitive material detecting gas; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 260nm, and the thickness of described Ni film is 15nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.2M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 1:5 and the mixed liquor of deionized water, and corrosion current is 20mA/cm
2, etching time is 1h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 100nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Test data:
In obtained device, DSSC 9 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 5 ~ 50nm in gas sensor; During test, this device is put into 1m
3light tight hermetical testing container, get 100mW/cm
2xenon source simulated solar irradiation, respectively to the NO passing into variable concentrations in test container
2gas.
The sensitivity of gas represents with following formula: R%=(I
0± I
t/ I
0) × 100%, in formula, when light source power is constant, I
0for not passing into NO
2time device in size of current, I
tfor passing into NO
2size of current during test gas in device.
Test obtains, the optimum transformation efficiency about 10.3% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 7.7%, reproducible; When gas sensor working temperature about 40 DEG C, it is all put up the best performance to the selectivity of gas and sensitivity, wherein, to NO
2the detection limit of gas is 16ppm, to the NO of 100ppm
2, sensitivity is 51, response time 21s; To NH
3the detection limit of gas is 13ppm, to the NH of 100ppm
3, sensitivity reaches 29, response time 17s.
Embodiment 4
A kind of Camp tent with high duplication gas detect that embodiments of the invention provide, the outer surface installation detecting device of this Camp tent, described checkout gear based on self energizing sensing element, and comprises data read module and gas identification module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter of particle is about 130nm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, and the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film together with porous silicon as the composite sensitive material detecting gas; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 350nm, and the thickness of described Ni film is 15nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 5ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 6ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 2:3 and the mixed liquor of deionized water, and corrosion current is 48mA/cm
2, etching time is 1h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 70nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Test data:
In obtained device, DSSC 8 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 20 ~ 40nm in gas sensor; During test, this device is put into 1m
3light tight hermetical testing container, get 100mW/cm
2xenon source simulated solar irradiation, respectively to the NO passing into variable concentrations in test container
2gas.
The sensitivity of gas represents with following formula: R%=(I
0± I
t/ I
0) × 100%, in formula, when light source power is constant, I
0for not passing into NO
2time device in size of current, I
tfor passing into NO
2size of current during test gas in device.
Test obtains, the optimum transformation efficiency about 8.7% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 7.4%, reproducible; When gas sensor working temperature about 40 DEG C, it is all put up the best performance to the selectivity of gas and sensitivity, wherein, to NO
2the detection limit of gas is 26ppm, to the NO of 100ppm
2, sensitivity is 39, response time 15s; To NH
3the detection limit of gas is 12ppm, to the NH of 100ppm
3, sensitivity reaches 37, response time 9s.
Embodiment 5
A kind of Camp tent with high duplication gas detect that embodiments of the invention provide, the outer surface installation detecting device of this Camp tent, described checkout gear based on self energizing sensing element, and comprises data read module and gas identification module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitization solar cell module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described comprised to electrode the stainless steel-based end, the conductive catalytic layer being close to the stainless steel-based end, the carbon nano-tube be arranged on described conductive catalytic layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass
2particle and dye molecules, described TiO
2the particle diameter of particle is about 150nm; Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrosion has Porous Silicon area, and the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film together with porous silicon as the composite sensitive material detecting gas; Described dye sensitization solar cell module and gas sensor module installation have a diameter to be the specification of the air admission hole of 0.5cm in surface be in the cuboid framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and make light anode upward, described gas sensor module, data read module are arranged at described lower portion, and described dye sensitization solar cell module, described gas sensor module are connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: the stainless steel-based end 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method plating Cr film and Ni film on the stainless steel-based end to form conductive catalytic layer, the thickness of described Cr film is 300nm, and the thickness of described Ni film is 15nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and injects the electrolyte in cavity, forms dye sensitization solar cell module;
The preparation of described gas sensor module comprises the following steps:
1. cutting silicon wafer substrate dimension is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 1:3 and the mixed liquor of deionized water, and corrosion current is 25mA/cm
2, etching time is 1h, forms the Porous Silicon area of size 1.5cm × 1cm on silicon chip substrate surface;
3. silicon chip substrate is put into magnetic control sputtering device, at its porous silicon region field surface evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate is put into tube furnace, passes into nitrogen under sealing normal pressure, utilizes CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method on Porous Silicon area, make the Au electrode of two round point shapes, the diameter of described Au electrode is 1mm, and thickness is 100nm.
Described data read module is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, described gas identification module is connected with described data read module by wire, described gas identification module is formed primarily of shell body and the gas detect component that is connected with shell body detachable, and described gas detect component is made up of diffusion control rete, instruction support powder and glass tube; The preparation process of described gas detect component is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
Test data:
In obtained device, DSSC 9 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 30 ~ 70nm in gas sensor; During test, this device is put into 1m
3light tight hermetical testing container, get 100mW/cm
2xenon source simulated solar irradiation, respectively to the NO passing into variable concentrations in test container
2gas.
The sensitivity of gas represents with following formula: R%=(I
0± I
t/ I
0) × 100%, in formula, when light source power is constant, I
0for not passing into NO
2time device in size of current, I
tfor passing into NO
2size of current during test gas in device.
Test obtains, the optimum transformation efficiency about 11.7% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 9.7%, reproducible; When gas sensor working temperature about 40 DEG C, it is all put up the best performance to the selectivity of gas and sensitivity, wherein, to NO
2the detection limit of gas is 14ppm, to the NO of 100ppm
2, sensitivity is 67, response time 15s; To NH
3the detection limit of gas is 25ppm, to the NH of 100ppm
3, sensitivity reaches 36, response time 23s.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (2)
1. have a Camp tent for high duplication gas detect, it is characterized in that: the outer surface installation detecting device of described Camp tent, this checkout gear based on self energizing sensing element, and comprises data read module and gas identification module, this self energizing sensing element comprises dye sensitization solar cell module (13) and gas sensor module (23), described dye sensitization solar cell module (13) comprises electrode, light anode and is filled in described to the electrolyte (30) between electrode and light anode, described comprised to electrode the stainless steel-based end (10), the conductive catalytic layer (20) being close to the stainless steel-based end (10), the carbon nano-tube (50) be arranged on described conductive catalytic layer (20), the TiO that described smooth anode comprises ITO electro-conductive glass substrate (40) and is positioned in ITO electro-conductive glass substrate (40)
2particle and dye molecules (60), described TiO
2the particle diameter of particle is about 150nm, and the described length to carbon nano-tube on electrode (50) is 15 μm, described gas sensor module (23) comprises silicon chip substrate (11), tungsten oxide nano (32) and Au electrode (31), on the surface of described silicon chip substrate (11), corrosion has Porous Silicon area (21), the surperficial evaporation of described Porous Silicon area has tungsten oxide layer film as the composite sensitive material detecting gas together with porous silicon, and the aperture of described porous silicon is 30 ~ 70nm, described dye sensitization solar cell module (13) and gas sensor module (23) are arranged at surface, and to have a diameter to be the specification of the air admission hole (53) of 0.5cm be in the cuboid framework (43) of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module (13) is bonded to the outer surface of described framework (53) by adhesive, and make light anode upward, described gas sensor module (23), it is inner that data read module (33) is arranged at described framework (53), described dye sensitization solar cell module (13), described gas sensor module (23) is connected by wire with data read module (33).
2. Camp tent according to claim 1, is characterized in that,
The making of described dye sensitization solar cell module (13) comprises the steps:
S1: prepared by electrode: the stainless steel-based end (10) 1. selecting thickness to be the specification of 0.3mm to be 5cm × 5cm, use sand paper polishing, through acetone, ethanol, deionized water successively ultrasonic cleaning; 2. utilize magnetron sputtering method to form conductive catalytic layer (20) at the stainless steel-based end (10) upper plating Cr film and Ni film, the thickness of described Cr film is 300nm, and the thickness of described Ni film is 15nm; 3. CVD is utilized, CH
4for carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully mix 50 DEG C of stirred in water bath, add butyl titanate 9ml in mixed solution, continue to stir 1h in a water bath, then add absolute ethyl alcohol 10ml, stir 1h in a water bath, leave standstill 12h, obtain TiO
2solution, is filtered, dry; 2. 5g step 1. middle dry TiO is got
2particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar grinding fully, obtained TiO
2slurry; 3. get step 2. in appropriate TiO
2slurry blade coating specification is after cleaning in the ITO electro-conductive glass substrate (40) of 5cm × 5cm, processes 2h, is then immersed in 6h in the ethanolic solution of N719, obtain light anode at 110 DEG C;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methylimidazole salt compounded of iodine, solvent is acetonitrile and the propylene carbonate mixed liquor of volume ratio 1:1;
S4: assembling: will cover on light anode to electrode, form the cavity of 50 μm between the two, edge utilizes insulator to encapsulate, and is injected in cavity by electrolyte (30), forms dye sensitization solar cell module (13);
The preparation of described gas sensor module (23) comprises the following steps:
1. cutting silicon wafer substrate (11) size is to 2cm × 2cm, puts into cleaning fluid ultrasonic cleaning 40min, 98% concentrated sulfuric acid and 40% hydrogen peroxide of cleaning fluid to be volume ratio be 3:1; Take out silicon chip substrate (11) deionized water rinsing clean, then put into hydrofluoric acid and soak 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid is the hydrofluoric acid (40%) of volume ratio 1:3 and the mixed liquor of deionized water, and corrosion current is 45mA/cm
2, etching time is 1h, forms the Porous Silicon area (21) of size 1.5cm × 1cm on silicon chip substrate (11) surface;
3. silicon chip substrate (11) is put into magnetic control sputtering device, at its Porous Silicon area (21) surperficial evaporation one deck tungsten film, thickness is 200nm, then silicon chip substrate (11) is put into tube furnace, pass into nitrogen under sealing normal pressure, utilize CVD 450 DEG C to grow tungsten oxide nano;
4. use magnetron sputtering method at the Au electrode (31) of Porous Silicon area (21) upper making two round point shapes, the diameter of described Au electrode (31) is 1mm, and thickness is 100nm.
Described data read module (33) is sent to the controller module being arranged at described checkout gear inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described checkout gear is transferred to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module (70), described gas identification module (70) is connected with described data read module (33) by wire, described gas identification module (70) is formed primarily of shell body (71) and the gas detect component (72) that is connected with shell body (71) detachable, and described gas detect component (72) is made up of diffusion control rete (73), instruction support powder (74) and glass tube (75); The preparation process of described gas detect component (72) is as follows:
S1: the process of carrier and activation: the silica-gel carrier sieved (90 ~ 100 order) is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, bottle stand-by;
S2: the preparation of instruction carrier: the original liquid of measured amounts puts into a container, pours a certain amount of activated carrier into, limit edged stirs, until mix, till supernatant liquor is less.In atmosphere after natural drying, load in closed container stand-by;
S3: the preparation of glass tube: select the glass tube (specification is ID2.0mm × OD4.0mm) that internal diameter is even, transparency is good, intercept into the glass tube some sections that length is 30mm, with sand paper by both sides hacking, then use suds, clear water, distilled water that glass tube cleaning is clean successively, dry stand-by;
S4: the preparation of diffusion control film: adopt the thick polyester film of 0.5mm as diffusion control film, after polymer PET drying, becomes external diameter to be the circular membrane of 2.0mm with mould punching;
S5: the assembling of gas identification module: side diffusion control film adhesive being adhered to glass tube, then takes a certain amount of instruction support powder and slowly loads to glass tube tight in glass tube, smooth rear bonding opposite side diffusion control film.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1438480A (en) * | 2002-02-10 | 2003-08-27 | 王宝辉 | Portable direct-reading type power-free hydrogen-sulfide gas detector and preparation of indicating matter |
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