CN105674192A - Solar street lamp with high-sensitivity detecting function - Google Patents

Solar street lamp with high-sensitivity detecting function Download PDF

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Publication number
CN105674192A
CN105674192A CN201610022374.2A CN201610022374A CN105674192A CN 105674192 A CN105674192 A CN 105674192A CN 201610022374 A CN201610022374 A CN 201610022374A CN 105674192 A CN105674192 A CN 105674192A
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module
gas
film
electrode
solar cell
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CN201610022374.2A
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Chinese (zh)
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蔡雄
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Individual
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Priority to CN201610022374.2A priority Critical patent/CN105674192A/en
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S9/00—Lighting devices with a built-in power supply; Systems employing lighting devices with a built-in power supply
    • F21S9/02—Lighting devices with a built-in power supply; Systems employing lighting devices with a built-in power supply the power supply being a battery or accumulator
    • F21S9/03—Lighting devices with a built-in power supply; Systems employing lighting devices with a built-in power supply the power supply being a battery or accumulator rechargeable by exposure to light
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S8/00—Lighting devices intended for fixed installation
    • F21S8/08—Lighting devices intended for fixed installation with a standard
    • F21S8/085—Lighting devices intended for fixed installation with a standard of high-built type, e.g. street light
    • F21S8/088—Lighting devices intended for fixed installation with a standard of high-built type, e.g. street light with lighting device mounted on top of the standard, e.g. for pedestrian zones
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V33/00—Structural combinations of lighting devices with other articles, not otherwise provided for
    • F21V33/0064—Health, life-saving or fire-fighting equipment
    • F21V33/0076—Safety or security signalisation, e.g. smoke or burglar alarms, earthquake detectors; Self-defence devices
    • 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
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • 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
    • 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
    • H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21W—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
    • F21W2131/00—Use or application of lighting devices or systems not provided for in codes F21W2102/00-F21W2121/00
    • F21W2131/10—Outdoor lighting
    • F21W2131/103—Outdoor lighting of streets or roads
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
    • Y02B20/72—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps in street lighting
    • 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 solar street lamp with a high-sensitivity detecting function. A detecting device is mounted on the external surface of the solar street lamp, is based on a self-energy-supply sensing element, and includes a data reading module and a gas identifying module; the self-energy-supply sensing element includes a dye sensitization solar battery module and a gas sensor module; the dye sensitization solar battery module serves as a working power supply of the gas sensor module to generate a self-energy-supply effect; the quick detection of specific harmful gas in the working environment of the solar street lamp can be realized; and the sensitivity is high.

Description

A kind of solar street light with highly sensitive measuring ability
Technical field
The present invention relates to street lamp field, more specifically relate to a kind of solar street light with highly sensitive measuring ability.
Background technology
Solar energy is the reproducible environmental protection energy of a kind of cleanliness without any pollution, utilizes solar electrical energy generation, has unrivaled clearClean property, tight security etc. Solar street light is to adopt solar cell for supplying power, and ultra-high brightness LED light fixture is as light source, andBy intelligent charging-discharging controller control, for substituting the street lamp of conventional electric power illumination.
Can be widely used in the places such as arterial street, community, factory, parking lot due to solar street light, different application regionsIt is proposed to different functional requirements, such as measuring ability to specific gas etc.
Summary of the invention
The object of the invention is to avoid weak point of the prior art and a kind of solar energy with highly sensitive measuring ability is providedStreet lamp.
Object of the present invention is achieved through the following technical solutions:
There is a solar street light for highly sensitive measuring ability, the outer surface installation detecting device of this solar street light, described inCheckout gear is based on self energizing sensing element, and this self energizing sensing element comprises dye sensitization solar cell module and gas sensingDevice module; Dye sensitization of solar module can be used as the working power of gas sensor module, and it is produced to self-energizing effect,And then can realize the fast detecting to specific pernicious gas in solar street light institute applied environment, highly sensitive, and repeatabilityHeight reaches the object of efficiently utilizing solar energy simultaneously.
Described dye sensitization solar cell module comprises electrode, light anode and is filled in described between electrode and light anodeElectrolyte, described to electrode comprise the stainless steel-based end, be close to the stainless steel-based end conduction Catalytic Layer, be arranged at described conduction and urgeChange the CNT on layer, described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, described TiO2The about 85nm of particle diameter of particle, described is 4 μ m to the length of CNT on electrode;Described gas sensor module comprises silicon chip substrate, tungsten oxide nano and Au electrode, on the surface of described silicon chip substrate, corrodesHave porous silicon region, the surperficial evaporation in described porous silicon region has tungsten oxide layer film answering as detection gas together with porous siliconClose sensitive material, the aperture of described porous silicon is 20～50nm; Described dye sensitization solar cell module and gas sensor mouldPiece is arranged at surface, and to have a diameter be the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cmIn, described dye sensitization solar cell module is bonded to the outer surface of described framework by adhesive, and makes light anode upward,Described gas sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module,Described gas sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 300nm, and the thickness of described Ni film is 15nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 1:3 and go fromThe mixed liquor of sub-water, corrosion current is 45mA/cm2, etching time is 1h, form on silicon chip substrate surface big or small 1.5cm ×The porous silicon region of 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 100nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED 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,The energy of working sensor is provided with DSSC; DSSC and porous silicon-base gas are passedSensor series connection, comprises solar module, sensor assembly, data read module and gas detection module; Solar cellBe used as the working power of sensor by solar electrical energy generation, gas sensor is produced to self-energizing effect, maximum usingSolar energy resources, has reduced energy waste and environmental pollution.
(2) DSSC to electrode in, conventionally adopt Pt as to electrode catalyst agent material, but platinum isA kind of noble metal, expensive, the present invention adopts CNT to substitute Pt as catalyst, makes simply, and catalytic efficiency is high,Cheap; Preparation cost reduces greatly, is conducive to widely popularize application; In addition, in the present invention, gas sensor module adoptsPorous silicon is sensitive material, and simultaneously at porous silicon surface evaporation tungsten oxide layer film, porous silica material is combined work with tungsten oxide materialFor composite sensing material, the situation of change of gas in environment-identification, highly sensitive, convenient and swift fast.
(3) the present invention is provided with the gas identification module that can identify gas type, this module after data read moduleThe instruction support powder using in the gas detection means of middle setting is judged gas type fast, when its work operation, does not need to dyeMaterial sensitization solar battery module provides energy, and entirety is economized and saved the energy, and has realized passive detection emission gases; Hurry upPrompt convenient.
Brief description of the drawings
Utilize accompanying drawing to be described further invention, but embodiment in accompanying drawing does not form any limitation of the invention, for thisThe those of ordinary skill in field, is not paying under the prerequisite of creative work, can also obtain according to the following drawings other accompanying drawing.
Fig. 1 is the schematic diagram of solar street light 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 is the combination schematic diagram of dye sensitization solar cell module of the present invention and gas sensor module.
Fig. 6 is the structural representation of gas identification module of the present invention.
Detailed description of the invention
In general,, after the gas component of the sensing element in gas sensor in extraneous test environment changes, it is correspondingMeasured physical quantity also can change, gas sensor detects the specific gas componant changing, and soAfter transformed the variation of the signal of telecommunication that reflection gas componant changes, such as resistance, electric capacity, dielectric etc.
Porous silicon is a kind of material with open structure, its can be by monocrystalline silicon or polysilicon oxidized making in hydrofluoric acid.Porous silicon has the advantages such as good optical property, huge surface area, and at present, porous silicon is to humidity, organic gas, NOX、COX、O2, HCl etc. shows detection. Gas sensor taking porous silicon as sensitive material is mainly to utilize its adsorbed gasAfter body, the variation of electrical conductivity detects gas. In the time that porous silicon is placed in detected gas environment, gas can be sent out at porous silicon surfaceRaw suction-operated, gas molecule can be captured hole or electronics from porous silicon surface, causes the resistance of porous silicon to change, and passes throughMeasure the variation that porous silicon resistance or the electric variation of leading can record gas concentration to be measured.
There is following technical problem in the gas sensor in correlation technique at present: in the time working, need external electricity at gas sensorSource or battery drive its work, use in a large number battery can cause environmental pollution and energy waste, and environment is had to potential harm,Therefore, need to seek a kind of new gas sensor of environmental protection and energy saving. Solar energy, as the continuable novel energy of one, is peopleThe basis of class survival and development. In future, solar electrical energy generation will become the main energy sources form of human society. At present, solar-electricityPond is mainly with silicon solar cell, DSSC and organic solar batteries form, wherein, most of on marketThat monocrystalline and polysilicon are the silicon solar cell of representative, although it has advantages of that transformation efficiency is high, stable performance, systemWhen standby silicon solar cell, refine high-purity silicon material and need to expend mass energy.
Under solar light irradiation, dye molecule absorbs luminous energy, and it is excited to excitation state by eigenstate, due to the shakiness of excitation stateFixed, its excitation state electrons is transferred to Nanometer Semiconductor Films from dye molecule and passes through the conductive layer of light anode, and then arrives dispatch from foreign news agencyRoad; Lose I in the electrolyte that the dye molecule of electronics can be close to-Revert to eigenstate, and I-Ion is oxidized to I3-, electronicsBe transferred to electrode from external circuit, under the effect of catalyst, by I in electrolyte3-Be reduced to I-, so circulation.
Based on this, the operation principle of device of the present invention is: DSSC and gas sensor, data read moduleSeries connection. Under solar radiation, in DSSC, dye molecule absorbs luminous energy, be excited, and the electronics process of releaseLight anode flows to external circuit, forms loop by porous silicon-base gas sensor, data detection module, to electrode, passes through carbonThe catalytic action of nanotube, goes back I in original electrolyte3-Ion, so forms working cycles; For gas sensor, detectedUnder gaseous environment, porous silicon and tungsten oxide can adsorption gas molecules, cause its electrical conductivity to change, and then act on electric currentChange, now data monitoring module can detect variation, finally shows in real time this gas concentration.
The invention provides a kind of solar street light with highly sensitive measuring ability, the outer surface installation and measuring of this solar street lightDevice, described checkout gear is based on self energizing sensing element, and this self energizing sensing element comprises dye sensitization solar cell moduleAnd gas sensor module; Dye sensitization of solar module can be used as the working power of gas sensor module, and it is produced certainlyThe effect of energy supply, and then can realize the fast detecting to specific pernicious gas in solar street light institute applied environment, it is highly sensitive,And repeatability is high, reaches the object of efficiently utilizing solar energy simultaneously.
In conjunction with legend, the present invention is made and being further illustrated:
Fig. 1 is solar street light schematic diagram of the present invention. Checkout gear 2 is installed on the outer surface of solar street light 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 is the combination schematic diagram of dye sensitization solar cell module of the present invention and gas sensor module.
Fig. 6 is the structural representation of gas identification module of the present invention.
Wherein: the stainless steel-based end of 10-, 11-silicon chip substrate, 12-silicon chip substrate, 13-dye sensitization solar cell module, 20-conduction is urgedChange layer, 21-porous silicon region, 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-is to CNT on electrode, 53-air admission hole, 60-TiO2Particle layer and dye molecule layer, 70-gas identification module, 71-shell body, 72-gas detection means, 73-DIFFUSION CONTROLLED rete,74-indicates support powder, 75-glass tube.
The invention will be further described with the following Examples.
Embodiment 1
A kind of solar street light with highly sensitive measuring ability that embodiments of the invention provide, the outside of this solar street lightSurface installation detecting device, described checkout gear is based on self energizing sensing element, and comprises that data read module and gas knowsOther module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitizationSolar module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described rightElectrode comprises the stainless steel-based end, is close to the conduction Catalytic Layer at the stainless steel-based end, is arranged at the CNT in described conduction Catalytic Layer,Described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, instituteState TiO2The about 85nm of particle diameter of particle; 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 region, the surperficial evaporation in described porous silicon region to have tungsten oxide layer film with manyHole silicon is together as the composite sensing material that detects gas; Described dye sensitization solar cell module and gas sensor module are establishedBeing placed in surface, to have a diameter be in the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cm, instituteState dye sensitization solar cell module and be bonded to the outer surface of described framework by adhesive, and make light anode upward, described gasBody sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module, described gasBody sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 500nm, and the thickness of described Ni film is 10nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 1:3 and go fromThe mixed liquor of sub-water, corrosion current is 45mA/cm2, etching time is 1h, form on silicon chip substrate surface big or small 1.5cm ×The porous silicon region of 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 100nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
Test data:
In obtained device, the length to CNT on electrode of DSSC is about 4 μ m, gas sensorApproximately 20～50nm of the aperture of middle porous silicon; When test, this device is put into 1m3Light tight airtight test container, get 100 mW/cm2Xenon source simulated solar irradiation, respectively to the NO that passes into variable concentrations in test container2Gas.
The sensitivity of gas represents with following formula: R%=(I0±It/I0) × 100%, in formula, in the situation that light source power is constant, I0For not passing into NO2Time size of current in device, ItFor passing into NO2Size of current when test gas in device.
Test obtains, the optimum transformation efficiency approximately 11.6% of DSSC, and test repeats 2000 times and finds afterwards,DSSC transformation efficiency drops to 10.3%, reproducible; In the time of approximately 40 DEG C of gas sensor operating temperatures,Its selective and sensitivity to gas is all put up the best performance, wherein, and to NO2The detection limit of gas is 5ppm, to 100ppmNO2, sensitivity is 62, response time 7s; To NH3The detection limit of gas is 5ppm, to the NH of 100ppm3，Sensitivity reaches 56, response time 4s.
Embodiment 2:
A kind of solar street light with highly sensitive measuring ability that embodiments of the invention provide, the outside of this solar street lightSurface installation detecting device, described checkout gear is based on self energizing sensing element, and comprises that data read module and gas knowsOther module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitizationSolar module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described rightElectrode comprises the stainless steel-based end, is close to the conduction Catalytic Layer at the stainless steel-based end, is arranged at the CNT in described conduction Catalytic Layer,Described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, instituteState TiO2The about 45nm of particle diameter of particle; 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 region, the surperficial evaporation in described porous silicon region to have tungsten oxide layer film with manyHole silicon is together as the composite sensing material that detects gas; Described dye sensitization solar cell module and gas sensor module are establishedBeing placed in surface, to have a diameter be in the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cm, instituteState dye sensitization solar cell module and be bonded to the outer surface of described framework by adhesive, and make light anode upward, described gasBody sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module, described gasBody sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 260nm, and the thickness of described Ni film is 7nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 30 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 2:3 and go fromThe mixed liquor of sub-water, corrosion current is 40mA/cm2, etching time is 2h, form on silicon chip substrate surface big or small 1.5cm ×The porous silicon region of 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 400nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
Test data:
In obtained device, the length to CNT on electrode of DSSC is about 7 μ m, gas sensorApproximately 5～25nm of the aperture of middle porous silicon; When test, this device is put into 1m3Light tight airtight test container, get 100mW/cm2Xenon source simulated solar irradiation, respectively to the NO that passes into variable concentrations in test container2Gas.
The sensitivity of gas represents with following formula: R%=(I0±It/I0) × 100%, in formula, in the situation that light source power is constant, I0For not passing into NO2Time size of current in device, ItFor passing into NO2Size of current when test gas in device.
Test obtains, the optimum transformation efficiency approximately 10.2% of DSSC, and test repeats 2000 times and finds afterwards,DSSC transformation efficiency drops to 8.1%, reproducible; In the time of approximately 40 DEG C of gas sensor operating temperatures,Its selective and sensitivity to gas is all put up the best performance, wherein, and to NO2The detection limit of gas is 11ppm, to 100ppmNO2, sensitivity is 52, response time 15s; To NH3The detection limit of gas is 9ppm, to the NH of 100ppm3，Sensitivity reaches 50, response time 6s.
Embodiment 3
A kind of solar street light with highly sensitive measuring ability that embodiments of the invention provide, the outside of this solar street lightSurface installation detecting device, described checkout gear is based on self energizing sensing element, and comprises that data read module and gas knowsOther module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitizationSolar module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described rightElectrode comprises the stainless steel-based end, is close to the conduction Catalytic Layer at the stainless steel-based end, is arranged at the CNT in described conduction Catalytic Layer,Described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, instituteState TiO2The about 55nm of particle diameter of particle; 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 region, the surperficial evaporation in described porous silicon region to have tungsten oxide layer film with manyHole silicon is together as the composite sensing material that detects gas; Described dye sensitization solar cell module and gas sensor module are establishedBeing placed in surface, to have a diameter be in the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cm, instituteState dye sensitization solar cell module and be bonded to the outer surface of described framework by adhesive, and make light anode upward, described gasBody sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module, described gasBody sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 260nm, and the thickness of described Ni film is 15nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.2M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 2:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 3:5 and go fromThe mixed liquor of sub-water, corrosion current is 20mA/cm2, etching time is 1h, form on silicon chip substrate surface big or small 1.5cm ×The porous silicon region of 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 100nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
Test data:
In obtained device, the length to CNT on electrode of DSSC is about 9 μ m, gas sensorApproximately 5～50nm of the aperture of middle porous silicon; When test, this device is put into 1m3Light tight airtight test container, get 100mW/cm2Xenon source simulated solar irradiation, respectively to the NO that passes into variable concentrations in test container2Gas.
The sensitivity of gas represents with following formula: R%=(I0±It/I0) × 100%, in formula, in the situation that light source power is constant, I0For not passing into NO2Time size of current in device, ItFor passing into NO2Size of current when test gas in device.
Test obtains, the optimum transformation efficiency approximately 9.3% of DSSC, and test repeats 2000 times and finds afterwards, dyesMaterial sensitization solar battery transformation efficiency drops to 6.7%, reproducible; In the time of approximately 40 DEG C of gas sensor operating temperatures,Its selective and sensitivity to gas is all put up the best performance, wherein, and to NO2The detection limit of gas is 21ppm, to 100ppmNO2, sensitivity is 51, response time 21s; To NH3The detection limit of gas is 13ppm, to the NH of 100ppm3，Sensitivity reaches 29, response time 17s.
Embodiment 4
A kind of solar street light with highly sensitive measuring ability that embodiments of the invention provide, the outside of this solar street lightSurface installation detecting device, described checkout gear is based on self energizing sensing element, and comprises that data read module and gas knowsOther module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitizationSolar module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described rightElectrode comprises the stainless steel-based end, is close to the conduction Catalytic Layer at the stainless steel-based end, is arranged at the CNT in described conduction Catalytic Layer,Described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, instituteState TiO2The about 80nm of particle diameter of particle; 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 region, the surperficial evaporation in described porous silicon region to have tungsten oxide layer film with manyHole silicon is together as the composite sensing material that detects gas; Described dye sensitization solar cell module and gas sensor module are establishedBeing placed in surface, to have a diameter be in the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cm, instituteState dye sensitization solar cell module and be bonded to the outer surface of described framework by adhesive, and make light anode upward, described gasBody sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module, described gasBody sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 350nm, and the thickness of described Ni film is 15nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 5ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 6ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 2:3 and go fromThe mixed liquor of sub-water, corrosion current is 37mA/cm2, etching time is 3h, form on silicon chip substrate surface big or small 1.5cm ×The porous silicon region of 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 70nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
Test data:
In obtained device, the length to CNT on electrode of DSSC is about 8 μ m, gas sensorApproximately 20～40nm of the aperture of middle porous silicon; When test, this device is put into 1m3Light tight airtight test container, get 100mW/cm2Xenon source simulated solar irradiation, respectively to the NO that passes into variable concentrations in test container2Gas.
The sensitivity of gas represents with following formula: R%=(I0±It/I0) × 100%, in formula, in the situation that light source power is constant, I0For not passing into NO2Time size of current in device, ItFor passing into NO2Size of current when test gas in device.
Test obtains, the optimum transformation efficiency approximately 8.7% of DSSC, and test repeats 2000 times and finds afterwards, dyesMaterial sensitization solar battery transformation efficiency drops to 7.4%, reproducible; In the time of approximately 40 DEG C of gas sensor operating temperatures,Its selective and sensitivity to gas is all put up the best performance, wherein, and to NO2The detection limit of gas is 18ppm, to 100ppmNO2, sensitivity is 9, response time 15s; To NH3The detection limit of gas is 12ppm, to the NH of 100ppm3，Sensitivity reaches 42, response time 12s.
Embodiment 5
A kind of solar street light with highly sensitive measuring ability that embodiments of the invention provide, the outside of this solar street lightSurface installation detecting device, described checkout gear is based on self energizing sensing element, and comprises that data read module and gas knowsOther module; This self energizing sensing element comprises dye sensitization solar cell module and gas sensor module; Described dye sensitizationSolar module comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode, described rightElectrode comprises the stainless steel-based end, is close to the conduction Catalytic Layer at the stainless steel-based end, is arranged at the CNT in described conduction Catalytic Layer,Described smooth anode comprises the substrate of ITO electro-conductive glass and is positioned at the suprabasil TiO of ITO electro-conductive glass2Particle and dye molecule layer, instituteState TiO2The about 100nm of particle diameter of particle; 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 region, the surperficial evaporation in described porous silicon region to have tungsten oxide layer film with manyHole silicon is together as the composite sensing material that detects gas; Described dye sensitization solar cell module and gas sensor module are establishedBeing placed in surface, to have a diameter be in the cuboid framework of the specification of the air admission hole of the 0.5cm aluminum that is 5cm × 5cm × 1cm, instituteState dye sensitization solar cell module and be bonded to the outer surface of described framework by adhesive, and make light anode upward, described gasBody sensor module, data read module are arranged at described framework inside, described dye sensitization solar cell module, described gasBody sensor module is connected by wire with data read module.
Preferably, the making of described dye sensitization solar cell module comprises the steps:
S1: prepared by electrode: 1. selecting thickness is the stainless steel-based end that the specification of 0.3mm is 5cm × 5cm, throws with sand paperLight, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method plating on the stainless steel-based endCr film and Ni film form conduction Catalytic Layer, and the thickness of described Cr film is 300nm, and the thickness of described Ni film is 15nm; 3. profitUse CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 6ml ethanol, 5ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cmUpper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid is volume ratioFor 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate and rinse well by deionized water, then put into hydrofluoric acid and soakBubble 10min, more successively with acetone, ethanol, deionized water ultrasonic cleaning 20min respectively;
2. adopt electrochemical process corrosion of silicon, preparation corrosive liquid, corrosive liquid be the hydrofluoric acid (40%) of volume ratio 1:3 and go fromThe mixed liquor of sub-water, corrosion current is 33mA/cm2, etching time is 1.5h, forms big or small 1.5cm on silicon chip substrate surfaceThe porous silicon region of × 1cm;
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, under sealing normal pressure, pass into nitrogen, utilize 450 DEG C of growth tungsten oxide nanometers of CVD methodLine;
4. use magnetron sputtering method on porous silicon region, to make the Au electrode of two round point shapes, the diameter of described Au electrode is 1Mm, thickness is 100nm.
Described data read module is sent to the controller module that is arranged at described checkout gear inside, institute by wireless communication moduleState controller module by wireless communication module and GPRS module communication, and the data value being detected by described checkout gear is passedTransport to detection data basestation;
Further, described self energizing sensing element is also provided with a gas identification module, and described gas identification module is by leadingLine is connected with described data read module, and described gas identification module is mainly by shell body and the gas being connected with shell body detachableDetection means forms, and described gas detection means is made up of DIFFUSION CONTROLLED rete, instruction support powder and glass tube; Described gasThe preparation process of detection means is as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes certainIt is interior to glass tube tight that amount instruction support powder slowly packs glass tube into, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
Test data:
In obtained device, the length to CNT on electrode of DSSC is about 9 μ m, gas sensorApproximately 30～70nm of the aperture of middle porous silicon; When test, this device is put into 1m3Light tight airtight test container, get 100mW/cm2Xenon source simulated solar irradiation, respectively to the NO that passes into variable concentrations in test container2Gas.
The sensitivity of gas represents with following formula: R%=(I0±It/I0) × 100%, in formula, in the situation that light source power is constant, I0For not passing into NO2Time size of current in device, ItFor passing into NO2Size of current when test gas in device.
Test obtains, the optimum transformation efficiency approximately 11.7% of DSSC, and test repeats 2000 times and finds afterwards,DSSC transformation efficiency drops to 9.7%, reproducible; In the time of approximately 40 DEG C of gas sensor operating temperatures,Its selective and sensitivity to gas is all put up the best performance, wherein, and to NO2The detection limit of gas is 14ppm, to 100ppmNO2, sensitivity is 45, response time 15s; To NH3The detection limit of gas is 25ppm, to the NH of 100ppm3，Sensitivity reaches 32, response time 23s.
Finally it should be noted that above embodiment is only in order to technical scheme of the present invention to be described, but not to protection domain of the present inventionRestriction, although the present invention has been done to explain with reference to preferred embodiment, those of ordinary skill in the art should be appreciated thatCan modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.

Claims (2)

1. a solar street light with highly sensitive measuring ability, is characterized in that: the outer surface peace of described solar street lightDress checkout gear, this checkout gear is 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 dyestuff is quickChanging solar module (13) comprises electrode, light anode and is filled in described to the electrolyte between electrode and light anode(30), described to electrode comprise the stainless steel-based end (10), be close to the stainless steel-based end (10) conduction Catalytic Layer (20), arrangeCNT (50) in described conduction Catalytic Layer (20), described smooth anode comprises ITO electro-conductive glass substrate (40) and positionTiO in ITO electro-conductive glass substrate (40)2Particle and dye molecule layer (60), described TiO2The about 85nm of particle diameter of particle,The described length to CNT on electrode (50) is 4 μ m; Described gas sensor module (23) comprise 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 region (21),The surperficial evaporation in described porous silicon region has tungsten oxide layer film composite sensing material as detection gas together with porous silicon, instituteThe aperture of stating porous silicon is 20～50nm; Described dye sensitization solar cell module (13) and gas sensor module (23)Being arranged at surface, to have a diameter be the cuboid frame of the specification of the air admission hole (53) of the 0.5cm aluminum that is 5cm × 5cm × 1cmIn frame (43), described dye sensitization solar cell module (13) is bonded to the appearance of described framework (53) by adhesiveFace, and make light anode upward, described gas sensor module (23), data read module (33) are arranged at described framework (53)Inside, described dye sensitization solar cell module (13), described gas sensor module (23) and data read module (33)Connect by wire.
2. solar street light 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: 1. selecting thickness is the stainless steel-based end (10) that the specification of 0.3mm is 5cm × 5cm, usesSand paper polishing, through acetone, ethanol, deionized water ultrasonic cleaning successively; 2. utilize magnetron sputtering method in the stainless steel-based end (10)Upper plating Cr film and Ni film form conduction Catalytic Layer (20), and the thickness of described Cr film is 300nm, described Ni film thickDegree is 15nm; 3. utilize CVD method, CH4For carbon source, Ni is catalyst, carbon nano-tube;
S2: the preparation of light anode: 1. get respectively absolute ethyl alcohol 50ml, ethylene glycol amine 2ml, make 50 DEG C of stirred in water bathIt fully mixes, and adds butyl titanate 9ml in mixed solution, continues at stirred in water bath 1h, then adds absolute ethyl alcohol10ml, at stirred in water bath 1h, leaves standstill 12h, obtains TiO2Solution, is filtered, dry; 2. get 5g step 1. inDry TiO2Particle, 10ml ethanol, 2ml acetylacetone,2,4-pentanedione mix, and put into mortar and grind fully, make TiO2Slurry;3. get the appropriate TiO of step in 2.2The ITO electro-conductive glass substrate that the specification of slurry blade coating after cleaning is 5cm × 5cm(40) upper, at 110 DEG C, process 2h, be then immersed in 6h in the ethanolic solution of N719, obtain light anode;
S3: electrolyte quota: 0.5M lithium iodide, 0.06M iodine, the tertiary yl pyridines of 0.1M4-and 0.3M1-propyl group-3-methyl miaowAzoles 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 electrode, and form the cavity of 50 μ m between the two, edge utilizes insulator envelopeDress, is injected into electrolyte (30) in cavity, 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, to 2cm × 2cm, is put into cleaning fluid ultrasonic cleaning 40min, and cleaning fluid isVolume ratio is 98% concentrated sulfuric acid and 40% hydrogen peroxide of 3:1; Take out silicon chip substrate (11) and rinse well by deionized water, then putEnter and in hydrofluoric acid, 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 be the hydrofluoric acid (40%) of volume ratio 1:3 and go fromThe mixed liquor of sub-water, corrosion current is 45mA/cm2, etching time is 1h, forms size 1.5 on silicon chip substrate (11) surfaceThe porous silicon region (21) of cm × 1cm;
3. silicon chip substrate (11) is put into magnetic control sputtering device, at its porous silicon region (21) surperficial evaporation one deck tungsten film, thickDegree, for 200nm, is then put into silicon chip substrate (11) tube furnace, under sealing normal pressure, passes into nitrogen, utilizes 450 DEG C of CVD methodsGrowth tungsten oxide nano;
4. use magnetron sputtering method at porous silicon region (21) the upper Au electrode (31) of making two round point shapes, described Au electricityThe diameter of the utmost point (31) is 1mm, and thickness is 100nm.
Described data read module (33) is sent to the controller mould that is arranged at described checkout gear inside by wireless communication modulePiece, described controller module is by wireless communication module and GPRS module communication, and by the number being detected by described checkout gearTransfer to detection data basestation according to value;
Further, described self energizing sensing element is also provided with a gas identification module (70), described gas identification module (70)Be connected with described data read module (33) by wire, described gas identification module (70) mainly by shell body (71) andThe gas detection means (72) being connected with shell body (71) detachable forms, and described gas detection means (72) is by diffusion controlMasking layer (73), instruction support powder (74) and glass tube (75) form; The preparation step of described gas detection means (72)Rapid as follows:
S1: the processing of carrier and activation: the silica-gel carrier having sieved (90～100 order) is placed in 600 DEG C of Muffle furnaces and is forgedBurn 2h, cooling after, bottle stand-by;
S2: the preparation of instruction carrier: measure a certain amount of original liquid and put into a container, pour a certain amount of activated carrier into, limitEdged stirs, until mix, till supernatant liquor is less. After natural drying in air, pack in closed container stand-by;
S3: the preparation of glass tube: select the glass tube that internal diameter is even, transparency is good (specification is ID2.0mm × OD4.0mm),Intercept into length and be some sections of the glass tubes of 30mm, by both sides hacking, then use successively suds, clear water, distillation with sand paperWater is clean by glass tube cleaning, dries stand-by;
S4: the preparation of DIFFUSION CONTROLLED film: adopt the thick polyester film of 0.5mm as DIFFUSION CONTROLLED film, after polyester film is dry, useIt is the circular membrane of 2.0mm that mould punching becomes external diameter;
S5: the assembling of gas identification module: DIFFUSION CONTROLLED film is adhered to a side of glass tube with adhesive, then takes a certain amount of fingerShow that support powder slowly packs glass tube into interior to glass tube tight, smooth rear bonding opposite side DIFFUSION CONTROLLED film.
CN201610022374.2A 2016-01-13 2016-01-13 Solar street lamp with high-sensitivity detecting function Pending CN105674192A (en)

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