CN105466973B - A kind of safety barrier with quick detection function - Google Patents

A kind of safety barrier with quick detection function Download PDF

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CN105466973B
CN105466973B CN201610021358.1A CN201610021358A CN105466973B CN 105466973 B CN105466973 B CN 105466973B CN 201610021358 A CN201610021358 A CN 201610021358A CN 105466973 B CN105466973 B CN 105466973B
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module
gas
glass tube
gas sensor
porous silicon
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CN105466973A (en
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刘立忠
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Jiangshan Haiwei Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses a kind of safety barrier with quick detection function, by the way that in safety barrier outer surface installation detecting device, the detection means is based on self energizing sensing element, and also includes data read module and gas identification module；Self energizing sensing element includes dye sensitization solar cell module and gas sensor module, working power of the dye sensitization solar cell module as gas sensor module, produce the effect of self energizing, the quick detection to pernicious gas in safety barrier use environment can be realized, high sensitivity, it is convenient and swift, and solar energy is maximally utilized, save the energy.

Description

A kind of safety barrier with quick detection function
Technical field
The present invention relates to guardrail field, is more particularly to a kind of safety barrier with quick detection function.
Background technology
Guardrail is mainly used in the occasions such as house, highway, shopping centre, public place to personal safety and the guarantor of installations and facilities Shield and protection.Guardrail is visible everywhere in we live.
In the use environment of guardrail, the appearance of seal or dangerous gas is inevitably had, however, existing shield Column does not possess gas detection function.
The content of the invention
There is provided a kind of with quick detection function it is an object of the invention to avoid weak point of the prior art Safety barrier.
The purpose of the present invention is achieved through the following technical solutions：
A kind of safety barrier with quick detection function, the safety barrier outer surface installation detecting device, the inspection Survey device and be based on self energizing sensing element, and also include data read module and gas identification module；The self energizing sensing Part includes dye sensitization solar cell module and gas sensor module；Dye sensitization of solar module is as gas sensor The working power of module, produce the effect of self energizing, it is possible to achieve the quick inspection to pernicious gas in safety barrier working environment Survey, high sensitivity is convenient and swift, while reaches the purpose for efficiently utilizing solar energy.
The dye sensitization solar cell module includes to electrode, light anode and is filled in described to electrode and light sun Electrolyte between pole, it is described electrode is included stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at it is described CNT on conductive catalytic layer, the light anode include ITO electro-conductive glass substrate and in ITO electro-conductive glass substrates TiO2Particle and dye molecules, the TiO2The particle diameter of particle about 40nm, the length to CNT on electrode are 6 μm； The gas sensor module includes silicon chip substrate, tungsten oxide nano and Au electrodes, corrodes on the surface of the silicon chip substrate There is Porous Silicon area, the surface evaporation of the Porous Silicon area has tungsten oxide layer film with porous silicon together as detection gas Composite sensitive material, the aperture of the porous silicon is 6~30nm；The dye sensitization solar cell module and gas sensor Module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid framework Interior, the dye sensitization solar cell module, to the outer surface of the framework, and makes light anode upward by adhesive bonding, The gas sensor module, data read module are arranged at the lower portion, the dye sensitization solar cell module, The gas sensor module is connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
The present invention is advantageous in that：
(1) present invention is based on DSSC technology and gas sensor technology, designs the gas of self energizing Sensor, i.e., the energy of working sensor is provided with DSSC；By DSSC with it is porous Silicon substrate gas sensor is connected, including solar module, sensor assembly, data read module and gas detection module； Solar cell is used as the working power of sensor by solar power generation, and the effect of self energizing is produced to gas sensor, Solar energy resources has been maximally utilized, has reduced energy waste and environmental pollution.
(2) in DSSC in electrode, generally use Pt is used as to electrode catalyst agent material, still Platinum is a kind of noble metal, expensive, and the present invention substitutes Pt as catalyst using CNT, makes simple, catalytic efficiency Height, it is cheap；Prepare cost to substantially reduce, be advantageous to widely popularize application；In addition, gas sensor module is adopted in the present invention It is sensitive material with porous silicon, while tungsten oxide layer film, porous silica material and tungsten oxide material knot is deposited in porous silicon surface Cooperate as composite sensitive material, can in quick environment-identification gas situation of change, high sensitivity is convenient and swift.
(3) present invention is provided with a gas identification module that can identify gas type behind data read module, The instruction support powder used in the gas detection means set in the module quickly judges gas type, when its work is run Dye sensitization solar cell module is not needed to provide energy, overall save has saved the energy, and realizes passive detection row Deflation body；It is efficient and convenient.
Brief description of the drawings
Invention is described further using accompanying drawing, but the embodiment in accompanying drawing does not form any limitation of the invention, For one of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to the following drawings Its accompanying drawing.
Fig. 1 is safety barrier schematic diagram of the present invention.
Fig. 2 is the structural representation of the dye sensitization solar cell module of the present invention.
Fig. 3 is the gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of the gas sensor module of the present invention.
Fig. 5 is the dye sensitization solar cell module of the present invention and the combination schematic diagram of gas sensor module.
Fig. 6 is the structural representation of the gas identification module of the present invention.
Embodiment
In general, after gas component of the sensing element in gas sensor in extraneous test environment changes, Its physical quantity being measured accordingly can also change, and gas sensor detects the specific gas componant to change Come, and then converted 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 be oxidized by monocrystalline silicon or polysilicon in hydrofluoric acid To be made.Porous silicon has the advantages that good optical property, huge surface area, and at present, porous silicon is to humidity, You Jiqi Body, NOX、COX、O2, HCl etc. show detection property.Gas sensor using porous silicon as sensitive material, mainly inhaled using it The change of electrical conductivity carrys out detection gas after attached gas.When porous silicon is placed in detected gas environment, gas can be in porous silicon Suction-operated occurs for surface, and gas molecule can capture hole or electronics from porous silicon surface, cause the resistance of porous silicon to become Change, the change by measuring porous silicon resistor or conductance can measure the change of under test gas concentration.
Following technical problem be present in the gas sensor in presently relevant technology：Gas sensor at work, it is necessary to External power supply or battery drive its work, largely can cause environmental pollution and energy waste using battery, have to environment latent Harm, therefore, it is necessary to seek a kind of new gas sensor of environmental protection and energy saving.Solar energy is as a kind of sustainable new The energy, it is the basis of human survival and development.In future, solar power generation is by as the main energy sources form of human society.At present, Solar cell mainly in the form of silicon solar cell, DSSC and organic solar batteries, wherein, market The silicon solar cell that upper major part is monocrystalline and polysilicon is representative, although it has transformation efficiency high, stable performance excellent Point, but when preparing silicon solar cell, refining high-purity silicon material needs to expend mass energy.
Under sunshine irradiation, dye molecule absorbs luminous energy, and it is excited to excitation state by eigenstate, due to excitation state Unstable, its excitation state electrons is transferred to the conductive layer that Nanometer Semiconductor Films pass through light anode from dye molecule, and then To external circuit；The dye molecule for losing electronics can be by I in neighbouring electrolyte-Revert to eigenstate, and I-Ion is oxidized to I3-, electronics is transferred to electrode from external circuit, in the presence of catalyst, by I in electrolyte3-It is reduced to I-, so circulation.
Based on this, the operation principle of device of the present invention is：DSSC and gas sensor, digital independent Block coupled in series.Under sunlight, dye molecule absorbs luminous energy in DSSC, is excited, the electronics of release External circuit is flowed to by light anode, loop is formed by porous silicon-base gas sensor, data detection module, to electrode, warp The catalytic action of CNT is crossed, goes back I in original electrolyte3-Ion, it is thusly-formed working cycles；For gas sensor, in quilt Under detection gas environment, porous silicon and tungsten oxide meeting adsorption gas molecule, its electrical conductivity is caused to change, and then act on electricity The change of stream, now data monitoring module can detect change, finally show the gas concentration in real time.
The present invention provides a kind of safety barrier with quick detection function, safety barrier outer surface installation detection dress Put, the detection means is based on self energizing sensing element, and also includes data read module and gas identification module；The confession Energy sensing element includes dye sensitization solar cell module and gas sensor module；Dye sensitization of solar module is as gas The working power of body sensor module, produce the effect of self energizing, it is possible to achieve to pernicious gas in safety barrier working environment Quick detection, high sensitivity is convenient and swift, at the same reach efficiently utilize solar energy purpose.
Further explanation is made to the present invention with reference to legend：
Fig. 1 is safety barrier schematic diagram of the present invention.Detection means 2 is installed on the outer surface of safety barrier 1.
Fig. 2 is the structural representation of the dye sensitization solar cell module of the present invention.
Fig. 3 is the gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of the gas sensor module of the present invention.
Fig. 5 is the dye sensitization solar cell module of the present invention and the combination schematic diagram of gas sensor module.
Fig. 6 is the structural representation of the gas identification module of the present invention.
Wherein：The stainless steel bases of 10-, 11- silicon chip substrates, 12- silicon chip substrates, 13- dye sensitization solar cell modules, 20- conductive catalytic layers, 21- Porous Silicon areas, 23- gas sensor modules, 30- electrolyte, 31-Au electrodes, 32- tungsten oxides are received Rice noodles, 33- data read modules, 40-ITO electro-conductive glass substrates, 43- frameworks, 50- is to CNT on electrode, 53- air inlets Hole, 60-TiO2Particle layer and dye molecules, 70- gas identification modules, 71- shell bodies, 72- gas detection means, 73- expand Dissipate control film layer, 74- instruction support powders, 75- glass tubes.
The invention will be further described with the following Examples.
Embodiment 1
A kind of safety barrier with quick detection function that embodiments of the invention are provided, the safety barrier external table Face installation detecting device, the detection means are based on self energizing sensing element, and also include data read module and gas knowledge Other module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dyestuff is quick Changing solar module includes to electrode, light anode and is filled in the electrolyte between electrode and light anode, institute Stating includes stainless steel base, the conductive catalytic layer close to stainless steel base, the carbon that is arranged on the conductive catalytic layer to electrode Nanotube, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dyestuff point Sublayer, the TiO2The particle diameter of particle about 40nm,；The gas sensor module include silicon chip substrate, tungsten oxide nano and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer of oxygen Change composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and gas The specification that sensor assembly is arranged at surface and has the air admission hole of an a diameter of 0.5cm is the rectangular of 5cm × 5cm × 1cm aluminum In body framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light positive by adhesive bonding Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization of solar electricity for pole Pond module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 500nm, and the thickness of the Ni films is 10nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 6 μm, and gas passes The aperture of porous silicon about 6~30nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take 100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 11.9% of DSSC, and test is sent out after repeating 2000 times Existing, DSSC transformation efficiency drops to 9.8%, reproducible；When about 40 DEG C of gas sensor operating temperature When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 4ppm, to 100ppm NO2, sensitivity 72, response time 5s；To NH3The detection limit of gas is 5ppm, to 100ppm NH3, sensitivity reaches 56, response time 4s.
Embodiment 2：
A kind of safety barrier with quick detection function that embodiments of the invention are provided, the safety barrier external table Face installation detecting device, the detection means are based on self energizing sensing element, and also include data read module and gas knowledge Other module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dyestuff is quick Changing solar module includes to electrode, light anode and is filled in the electrolyte between electrode and light anode, institute Stating includes stainless steel base, the conductive catalytic layer close to stainless steel base, the carbon that is arranged on the conductive catalytic layer to electrode Nanotube, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dyestuff point Sublayer, the TiO2The particle diameter of particle about 35nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano and Au Electrode, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer of oxidation Composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and gas pass Sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid In framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light anode by adhesive bonding Upward, the gas sensor module, data read module are arranged at the lower portion, the DSSC Module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:3 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 40mA/cm2, etching time 2h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 60nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 7 μm, and gas passes The aperture of porous silicon about 5~20nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take 100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 10.2% of DSSC, and test is sent out after repeating 2000 times Existing, DSSC transformation efficiency drops to 8.1%, reproducible；When about 40 DEG C of gas sensor operating temperature When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 10ppm, right 100ppm NO2, sensitivity 72, response time 9s；To NH3The detection limit of gas is 9ppm, to 100ppm NH3, it is sensitive Degree is up to 50, response time 8s.
Embodiment 3
A kind of safety barrier with quick detection function that embodiments of the invention are provided, the safety barrier external table Face installation detecting device, the detection means are based on self energizing sensing element, and also include data read module and gas knowledge Other module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dyestuff is quick Changing solar module includes to electrode, light anode and is filled in the electrolyte between electrode and light anode, institute Stating includes stainless steel base, the conductive catalytic layer close to stainless steel base, the carbon that is arranged on the conductive catalytic layer to electrode Nanotube, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dyestuff point Sublayer, the TiO2The particle diameter of particle about 45nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano and Au Electrode, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer of oxidation Composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and gas pass Sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid In framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light anode by adhesive bonding Upward, the gas sensor module, data read module are arranged at the lower portion, the DSSC Module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:5 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 30mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 10 μm, gas The aperture of porous silicon about 5~50nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take 100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 10.9% of DSSC, and test is sent out after repeating 2000 times Existing, DSSC transformation efficiency drops to 8.7%, reproducible；When about 40 DEG C of gas sensor operating temperature When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 12ppm, right 100ppm NO2, sensitivity 51, response time 5s；To NH3The detection limit of gas is 13ppm, to 100ppm NH3, spirit Sensitivity is up to 9, response time 7s.
Embodiment 4
A kind of safety barrier with quick detection function that embodiments of the invention are provided, the safety barrier external table Face installation detecting device, the detection means are based on self energizing sensing element, and also include data read module and gas knowledge Other module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dyestuff is quick Changing solar module includes to electrode, light anode and is filled in the electrolyte between electrode and light anode, institute Stating includes stainless steel base, the conductive catalytic layer close to stainless steel base, the carbon that is arranged on the conductive catalytic layer to electrode Nanotube, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dyestuff point Sublayer, the TiO2The particle diameter of particle about 80nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano and Au Electrode, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer of oxidation Composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and gas pass Sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid In framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light anode by adhesive bonding Upward, the gas sensor module, data read module are arranged at the lower portion, the DSSC Module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 350nm, and the thickness of the Ni films is 15nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 6ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:3 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 48mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 70nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 8 μm, and gas passes The aperture of porous silicon about 20~40nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take 100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 8.7% of DSSC, and test is sent out after repeating 2000 times Existing, DSSC transformation efficiency drops to 7.4%, reproducible；When about 40 DEG C of gas sensor operating temperature When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 26ppm, right 100ppm NO2, sensitivity 39, response time 15s；To NH3The detection limit of gas is 12ppm, to 100ppm NH3, spirit Sensitivity is up to 37, response time 9s.
Embodiment 5
A kind of safety barrier with quick detection function that embodiments of the invention are provided, the safety barrier external table Face installation detecting device, the detection means are based on self energizing sensing element, and also include data read module and gas knowledge Other module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dyestuff is quick Changing solar module includes to electrode, light anode and is filled in the electrolyte between electrode and light anode, institute Stating includes stainless steel base, the conductive catalytic layer close to stainless steel base, the carbon that is arranged on the conductive catalytic layer to electrode Nanotube, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dyestuff point Sublayer, the TiO2The particle diameter of particle about 100nm；The gas sensor module include silicon chip substrate, tungsten oxide nano and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer of oxygen Change composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and gas The specification that sensor assembly is arranged at surface and has the air admission hole of an a diameter of 0.5cm is the rectangular of 5cm × 5cm × 1cm aluminum In body framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light positive by adhesive bonding Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization of solar electricity for pole Pond module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml, 1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2. The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak 10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go The mixed liquor of ionized water, corrosion current 25mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm × 1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is 200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube； The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces 2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm × OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying, The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 9 μm, and gas passes The aperture of porous silicon about 30~70nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take 100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 11.7% of DSSC, and test is sent out after repeating 2000 times Existing, DSSC transformation efficiency drops to 9.7%, reproducible；When about 40 DEG C of gas sensor operating temperature When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 14ppm, right 100ppm NO2, sensitivity 67, response time 15s；To NH3The detection limit of gas is 25ppm, to 100ppm NH3, spirit Sensitivity is up to 36, response time 23s.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention Matter and scope.

Claims (1)

  1. A kind of 1. safety barrier with quick detection function, it is characterised in that：The safety barrier outer surface installation detection Device, the detection means is based on self energizing sensing element, and also includes data read module and gas identification module；The confession Energy sensing element includes dye sensitization solar cell module (13) and gas sensor module (23)；The dye sensitization sun Energy battery module (13) includes to electrode, light anode and is filled in the electrolyte (30) between electrode and light anode, It is described electrode is included stainless steel base (10), close to stainless steel base (10) conductive catalytic layer (20), be arranged at described lead CNT (50) on Electrocatalytic Layer (20), the light anode include ITO electro-conductive glass substrate (40) and positioned at ITO conduction glass TiO in glass substrate (40)2Particle and dye molecules (60), the TiO2The particle diameter 40nm of particle, it is described that carbon on electrode is received The length of mitron (50) is 6 μm；The gas sensor module (23) include silicon chip substrate (11), tungsten oxide nano (32) and Au electrodes (31), on the surface of the silicon chip substrate (11) corrosion have Porous Silicon area (21), the surface of the Porous Silicon area Evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas, and the aperture of the porous silicon is 6 ~30nm；The dye sensitization solar cell module (13) and gas sensor module (23) be arranged at surface have it is one a diameter of The specification of 0.5cm air admission hole (53) is that the dye sensitization is too in the cuboid framework (43) of 5cm × 5cm × 1cm aluminum Outer surface of the positive energy battery module (13) by adhesive bonding to the framework (43), and make light anode upward, the gas Sensor assembly (23), data read module (33) are arranged at the framework (43) inside, the DSSC Module (13), the gas sensor module (23) and data read module (33) are connected by wire；
    The making of the dye sensitization solar cell module (13) comprises the following steps：
    S1：It is prepared by electrode：1. the stainless steel base (10) that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；It is 2. gold-plated in stainless steel base (10) using magnetron sputtering method Belong to Cr films and Ni films form conductive catalytic layer (20), the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；③ Utilize CVD, CH4For carbon source, Ni is catalyst, grows CNT；
    S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make its abundant in 50 DEG C of stirred in water bath Mixing, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, absolute ethyl alcohol 10ml is then added, in water 1h is stirred in bath, 12h is stood, obtains TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Particle, 10ml ethanol, the mixing of 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. appropriate in taking step 2. TiO2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrate (40), by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
    S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methylimidazoles Salt compounded of iodine, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
    S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge is encapsulated using insulator, Electrolyte (30) is injected into cavity, forms dye sensitization solar cell module (13)；
    The preparation of the gas sensor module (23) comprises the following steps：
    1. cutting silicon chip substrate (11) size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate (11) to be rinsed well with deionized water, place into hydrofluoric acid Middle immersion 10min, then it is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
    2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 40% hydrofluoric acid and deionized water Mixed liquor, corrosion current 45mA/cm2, etching time 1h, size 1.5cm × 1cm is formed on silicon chip substrate (11) surface Porous Silicon area (21)；
    3. silicon chip substrate (11) is put into magnetic control sputtering device, one layer of tungsten film, thickness is deposited on its Porous Silicon area (21) surface For 200nm, then silicon chip substrate (11) is put into tube furnace, seals and is passed through nitrogen under normal pressure, utilizes 450 DEG C of growths of CVD Tungsten oxide nano；
    4. the Au electrodes (31) of two round point shapes, the Au electrodes are made on Porous Silicon area (21) using magnetron sputtering method (31) a diameter of 1mm, thickness 100nm；
    The data read module (33) is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；
    Further, the self energizing sensing element is additionally provided with a gas identification module (70), the gas identification module (70) connected by wire and the data read module (33), the gas identification module (70) mainly by shell body (71) and The gas detection means (72) being detachably connected with shell body (71) are formed, and the gas detection means (72) control film by diffusion Layer (73), instruction support powder (74) and glass tube (75) are formed；The preparation process of the gas detection means (72) is as follows：
    S1：The processing and activation of carrier：The silica-gel carrier sieved is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, dress Bottle is stand-by, wherein, the specification of silica-gel carrier is 90~100 mesh；
    S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, pours into a certain amount of activated carrier, side Edged stirs, until it is well mixed, untill supernatant liquor is less, after spontaneously drying in atmosphere, it is fitted into stand-by in closed container；
    S3：The preparation of glass tube：Select the glass tube that internal diameter is uniform, transparency is good, specification is ID2.0mm × OD4.0mm, interception Into some sections of the glass tube that length is 30mm, with sand paper by both sides feather plucking, then successively with suds, clear water, distilled water by glass Glass pipe cleans up, and dries stand-by；
    S4：The preparation of diffusion control film：Using polyester film thick 0.5mm as diffusion control film, after polymer PET drying, mould is used Tool strikes out the circular membrane that external diameter is 2.0mm；
    S5：The assembling of gas identification module：The side of control film adhesive bonding to glass tube will be spread, then weighed certain Amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
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CN109056597A (en) * 2018-09-13 2018-12-21 北京城建十六建筑工程有限责任公司 A kind of assembled of traveling construction fence sytsem is unidirectionally turned track
CN109056593A (en) * 2018-09-13 2018-12-21 北京城建十六建筑工程有限责任公司 A kind of traveling construction fence sytsem with enclosing function

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