CN105527322A - High-sensitivity self-energizing automobile exhaust gas detection device - Google Patents

High-sensitivity self-energizing automobile exhaust gas detection device Download PDF

Info

Publication number
CN105527322A
CN105527322A CN201610021595.8A CN201610021595A CN105527322A CN 105527322 A CN105527322 A CN 105527322A CN 201610021595 A CN201610021595 A CN 201610021595A CN 105527322 A CN105527322 A CN 105527322A
Authority
CN
China
Prior art keywords
module
gas
electrode
solar cell
gas sensor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610021595.8A
Other languages
Chinese (zh)
Inventor
杨林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201610021595.8A priority Critical patent/CN105527322A/en
Publication of CN105527322A publication Critical patent/CN105527322A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/542Dye sensitized solar cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a high-sensitivity self-energizing automobile exhaust gas detection device. The detection device is based on a self-energizing sensing element and further comprises a data reading module and a gas recognition module; the self-energizing sensing element comprises a dye-sensitized solar cell module and a gas sensor module. The dye-sensitized solar cell module serves as a working power supply of the gas sensor module so as to generate a self-energizing effect, and the gas sensor module adopts a combination of a porous silicon material and a tungsten oxide material as a composite sensitive material, so that the condition of change of gases in an environment can be quickly recognized, the sensitivity is high, and the detection is convenient and fast.

Description

A kind of highly sensitive self-energizing automobile exhaust gas checking apparatus
Technical field
The present invention relates to environmental monitoring field, more specifically relate to a kind of highly sensitive self-energizing automobile exhaust gas checking apparatus.
Background technology
The productive life of people be unable to do without air, and the gas that whether there is threat health in air is most important for productive life.These threaten and include poisonous gas exists initiation environment public health problem potential danger to the injury of human body, the blast of flammable explosive gas leakage initiation and gas harmful gas.In these problems, the discharge of vehicle exhaust has caused a lot of environmental pollution accidents comprising photo-chemical smog, uses gas sensor to detect the emission behaviour of vehicle exhaust in the device of traditional detection vehicle exhaust.But, there is following technical matters 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 battery that uses can cause environmental pollution and energy dissipation, has potential harm to environment.Therefore, the new gas sensor seeking a kind of environmental protection and energy saving is needed.Sun power, as the continuable novel energy of one, is the basis of human survival and development.In future, solar electrical energy 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.
Summary of the invention
The object of the invention is to avoid weak point of the prior art and a kind of highly sensitive self-energizing automobile exhaust gas checking apparatus is provided.
Object of the present invention is achieved through the following technical solutions:
A kind of highly sensitive self-energizing automobile exhaust gas checking apparatus, is characterized in that: described pick-up unit 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 electrolytic solution 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 50nm, and the described length to carbon nano-tube on electrode is 5 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 5 ~ 30nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
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 sensor by solar electrical energy generation, produce self-energizing effect to gas sensor, and maximum using solar energy resources, decreases energy dissipation and environmental pollution.
(2) at 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 catalyzer, 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 structural representation of dye sensitization solar cell module of the present invention.
Fig. 2 is gas sensor module schematic top plan view of the present invention.
Fig. 3 is the sectional view of gas sensor module of the present invention.
Fig. 4 be dye sensitization solar cell module of the present invention and gas sensor module in conjunction with schematic diagram.
Fig. 5 is the structural representation of gas identification module of the present invention.
Embodiment
In general, after the gas composition of sensitive element 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 electric signal 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 hydrofluorite 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 matters 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 dissipation, to environment, there is potential harm, therefore, the new gas sensor seeking a kind of environmental protection and energy saving is needed.Sun power, as the continuable novel energy of one, is the basis of human survival and development.In future, solar electrical energy 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 sunlight, dye molecule absorbs luminous energy, and it is excited to excited state by eigenstate, and due to the instability of excited state, its excited 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 electrolytic solution 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 catalyzer, by I in electrolytic solution 3-be reduced to I -, so circulate.
Based on this, the principle of work of device of the present invention is: DSSC is connected with gas sensor, data read module.Under sunlight irradiates, 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 working 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.
In conjunction with legend the present invention made and further illustrating:
Fig. 1 is the structural representation of dye sensitization solar cell module of the present invention.
Fig. 2 is gas sensor module schematic top plan view of the present invention.
Fig. 3 is the sectional view of gas sensor module of the present invention.
Fig. 4 be dye sensitization solar cell module of the present invention and gas sensor module in conjunction with schematic diagram.
Fig. 5 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-electrolytic solution, 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-tail gas identification module, 71-shell body, 72-gas detect component, 73-diffusion controls rete, and 74-indicates support powder, 75-glass tube
The invention will be further described with the following Examples.
Embodiment 1
The highly sensitive self-energizing automobile exhaust gas checking apparatus of the one that embodiments of the invention provide, described pick-up unit 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 electrolytic solution 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 50nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
Test data:
In obtained device, DSSC 5 μm are about to the length of carbon nano-tube on electrode, the aperture of porous silicon about 5 ~ 30nm 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 9.3%, 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 4ppm, to the NO of 100ppm 2, sensitivity is 72, response time 5s; To NH 3the detection limit of gas is 3ppm, to the NH of 100ppm 3, sensitivity reaches 56, response time 4s.
Embodiment 2:
The highly sensitive self-energizing automobile exhaust gas checking apparatus of the one that embodiments of the invention provide, described pick-up unit 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 electrolytic solution 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 30nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (40%) of volume ratio 1:3 and the mixed liquor of deionized water, and corrosion current is 40mA/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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
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 ~ 20nm 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 11.2% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 9.1%, 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 10ppm, to the NO of 100ppm 2, sensitivity is 72, response time 5s; To NH 3the detection limit of gas is 9ppm, to the NH of 100ppm 3, sensitivity reaches 50, response time 4s.
Embodiment 3
The highly sensitive self-energizing automobile exhaust gas checking apparatus of the one that embodiments of the invention provide, described pick-up unit 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 electrolytic solution 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 40nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (40%) of volume ratio 1:5 and the mixed liquor of deionized water, and corrosion current is 30mA/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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
Test data:
In obtained device, DSSC 10 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 10.2% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 8.9%, 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 40, response time 5s; To NH 3the detection limit of gas is 13ppm, to the NH of 100ppm 3, sensitivity reaches 9, response time 7s.
Embodiment 4
The highly sensitive self-energizing automobile exhaust gas checking apparatus of the one that embodiments of the invention provide, described pick-up unit 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 electrolytic solution 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 80nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (40%) of volume ratio 2:3 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 tubular 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 80nm.
Described data read module is sent to the controller module being arranged at described pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
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 8.5% of DSSC, and find after test repetition 2000 times, DSSC transformation efficiency drops to 7.9%, 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 57, 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
The highly sensitive self-energizing automobile exhaust gas checking apparatus of the one that embodiments of the invention provide, described pick-up unit 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 electrolytic solution 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 100nm; 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 rectangular parallelepiped framework of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module is bonded to the outside surface of described framework by bonding agent, 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 catalyzer, 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 diacetone 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 sulphuric 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 hydrofluorite 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 hydrofluorite (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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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 controls rete, instruction support powder and glass tube form by spreading; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
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 9.3%, 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 14ppm, to the NO of 100ppm 2, sensitivity is 42, 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. a highly sensitive self-energizing automobile exhaust gas checking apparatus, is characterized in that: described pick-up unit 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 electrolytic solution (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 50nm, and the described length to carbon nano-tube on electrode (50) is 5 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 5 ~ 30nm, 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 rectangular parallelepiped framework (43) of the aluminum of 5cm × 5cm × 1cm, described dye sensitization solar cell module (13) is bonded to the outside surface of described framework (53) by bonding agent, 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. automobile exhaust gas checking apparatus 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 catalyzer, 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 diacetone 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 electrolytic solution (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 sulphuric 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 hydrofluorite 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 hydrofluorite (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 tubular 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 pick-up unit inside by wireless communication module, described controller module is communicated with GPRS module by wireless communication module, and the data value detected by described pick-up unit 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) controls rete (73), instruction support powder (74) and glass tube (75) by diffusion and forms; 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 controlling diaphragm: adopt the thick polyester film of 0.5mm as diffusion controlling diaphragm, 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 controlling diaphragm bonding agent 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 controlling diaphragm.
CN201610021595.8A 2016-01-13 2016-01-13 High-sensitivity self-energizing automobile exhaust gas detection device Pending CN105527322A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610021595.8A CN105527322A (en) 2016-01-13 2016-01-13 High-sensitivity self-energizing automobile exhaust gas detection device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610021595.8A CN105527322A (en) 2016-01-13 2016-01-13 High-sensitivity self-energizing automobile exhaust gas detection device

Publications (1)

Publication Number Publication Date
CN105527322A true CN105527322A (en) 2016-04-27

Family

ID=55769678

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610021595.8A Pending CN105527322A (en) 2016-01-13 2016-01-13 High-sensitivity self-energizing automobile exhaust gas detection device

Country Status (1)

Country Link
CN (1) CN105527322A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106018498A (en) * 2016-07-28 2016-10-12 电子科技大学 Self-powdered sensor for detecting automobile tail gas and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1280393A (en) * 1999-06-30 2001-01-17 佳能株式会社 Solar cell module
CN101587781A (en) * 2009-06-26 2009-11-25 大连理工大学 Process for preparing dye-sensitized solar cell by complete spray coating process
CN101907595A (en) * 2010-07-15 2010-12-08 合肥工业大学 Electrochemical CO gas sensor
WO2012070886A2 (en) * 2010-11-26 2012-05-31 Bioneer Corporation System for removing organic compounds from air
CN102831753A (en) * 2012-08-16 2012-12-19 上海霖睿自控设备有限公司 Solar gas detecting and alarming system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1280393A (en) * 1999-06-30 2001-01-17 佳能株式会社 Solar cell module
CN101587781A (en) * 2009-06-26 2009-11-25 大连理工大学 Process for preparing dye-sensitized solar cell by complete spray coating process
CN101907595A (en) * 2010-07-15 2010-12-08 合肥工业大学 Electrochemical CO gas sensor
WO2012070886A2 (en) * 2010-11-26 2012-05-31 Bioneer Corporation System for removing organic compounds from air
CN102831753A (en) * 2012-08-16 2012-12-19 上海霖睿自控设备有限公司 Solar gas detecting and alarming system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106018498A (en) * 2016-07-28 2016-10-12 电子科技大学 Self-powdered sensor for detecting automobile tail gas and preparation method thereof
CN106018498B (en) * 2016-07-28 2018-07-10 电子科技大学 It is a kind of for self energizing sensor of automobile emission gas analyzer and preparation method thereof

Similar Documents

Publication Publication Date Title
CN105529191A (en) High-conversion-efficiency solar cell based vehicle license plate recognition device of parking lot
TW558842B (en) Solar cell
CN102549835B (en) Dye-sensitised solar cell
CN102449844B (en) Dye-sensitized solar cell
CN105489385A (en) Electric vehicle charging station based on self-powering detecting function
CN105466973A (en) Safety guardrail with quick detection function
CN104076066A (en) Resistive hydrogen sensor based on nano composite material and preparation method thereof
CN105527322A (en) High-sensitivity self-energizing automobile exhaust gas detection device
CN105673377A (en) Metering refueling pump based on high-efficiency solar cell
CN105842287A (en) Nanomaterials used for detecting nitrogen dioxide and gas-sensitive sensor element
CN105489386A (en) Solar cell frame with quick gas detection function
CN105655137A (en) Outdoor communication device based on self-powered detection
CN105513810A (en) Oil tank with high-repetitiveness detection function of refueling station
CN105699436A (en) Exhaust gas detection device based on solar cell high in conversion rate
CN105674192A (en) Solar street lamp with high-sensitivity detecting function
CN105466974A (en) High voltage power supply capable of achieving rapid gas recognition function
CN105428077A (en) Outdoor illumination device based on high-efficiency solar battery
CN105513811A (en) Camping tent with high-repetitiveness gas detection function
CN105471364A (en) Photovoltaic power generation equipment based on gas identification function
CN105466052A (en) Solar water heater with high-repeatability detection function
CN105486820A (en) Outdoor video surveillance equipment with gas detection function
CN105551803A (en) Self-powered detection-based outdoor gas boiler
CN105529190A (en) Parking lot gate with self-energized gas detection function
CN105429596A (en) Product outdoor display device based on high-efficiency solar battery
CN105679545A (en) Rapid gas recognition function-based curtain

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160427

RJ01 Rejection of invention patent application after publication