CN105680250B - A kind of outdoor safety socket with highly sensitive identification function - Google Patents
A kind of outdoor safety socket with highly sensitive identification function Download PDFInfo
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- CN105680250B CN105680250B CN201610020716.7A CN201610020716A CN105680250B CN 105680250 B CN105680250 B CN 105680250B CN 201610020716 A CN201610020716 A CN 201610020716A CN 105680250 B CN105680250 B CN 105680250B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of outdoor safety sockets with highly sensitive identification function, and by the outer surface installation detecting device in safety socket, which is based on self energizing sensing element, and further 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, generate the effect of self energizing, it can realize the quick detection to pernicious gas in safety socket working environment, high sensitivity, repeatability are high.
Description
Technical field
The present invention relates to socket fields, are more particularly to a kind of outdoor safety socket with highly sensitive identification function.
Background technology
Socket refer to there are one or the seat that can be inserted into of more than one circuit connection, various wiring can be inserted by it, be convenient for
It is connected with other circuits.By the connection and disconnection between circuit and copper piece, come reach finally control the circuit connect through and off
It opens.
However, since the application range of existing safety socket is wide, when it is in different operating environment, it is proposed
New requirement functionally, such as detection function to hazardous gas.
The content of the invention
It is provided a kind of with highly sensitive identification function it is an object of the invention to avoid shortcoming of the prior art
Outdoor safety socket.
The purpose of the present invention is achieved through the following technical solutions：
A kind of outdoor safety socket with highly sensitive identification function, the outer surface installation detection dress of the safety socket
It puts, the detection device is based on self energizing sensing element, which includes dye sensitization solar cell module
And gas sensor module；Dye sensitization of solar module can generate it as the working power of gas sensor module
The effect of self energizing, and then can realize the quick detection to pernicious gas in safety socket working environment, high sensitivity, and
It is repeated high, while achieve the purpose that efficiently to utilize 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
Carbon nanotubes 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 grain size of particle about 450nm, the length to carbon nanotubes on electrode are 20 μ
m；The gas sensor module includes silicon chip substrate, tungsten oxide nano and Au electrodes, rotten on the surface of the silicon chip substrate
Erosion has Porous Silicon area, and the surface vapor deposition 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 20~60nm；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 frame, the dye sensitization solar cell module, to the outer surface of the frame, and makes light anode by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye-sensitized solar cells
Module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 carbon nanotubes；
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 being sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:It 3 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
The invention has the beneficial effects that：
(1) the present invention is based on dye-sensitized solar cells technology and gas sensor technology, the gas of self energizing is designed
Sensor provides the energy of working sensor with dye-sensitized solar cells；By dye-sensitized solar cells 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 generated to gas sensor,
Solar energy resources has been maximally utilized, has reduced energy waste and environmental pollution.
(2) in dye-sensitized solar cells 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 carbon nanotubes, makes simple, catalytic efficiency
Height, it is cheap；Manufacturing cost substantially reduces, and is conducive 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 efficient.
(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 work is run
Dye sensitization solar cell module is not required to provide energy, whole save has saved the energy, and realizes passive detection row
Deflation body；It is efficient and convenient.
Description of the drawings
Invention is described further using attached drawing, but the embodiment in attached drawing does not form any limitation of the invention,
For those of ordinary skill in the art, without creative efforts, can also it be obtained according to the following drawings
Its attached drawing.
Fig. 1 is the schematic diagram of safety socket of the present invention.
Fig. 2 is the structure diagram 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 structure diagram of the gas identification module of the present invention.
Specific 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 changed specific gas componant
Come, and then converted the variation of the electric signal of reflection gas componant variation, such as resistance, capacitance, dielectric etc..
Porous silicon is a kind of material with open structure, can be aoxidized by monocrystalline silicon or polysilicon in hydrofluoric acid
To be made.Porous silicon has many advantages, such as 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.Using porous silicon as the gas sensor of sensitive material, mainly inhaled using it
The variation 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, the resistance of porous silicon is caused to become
Change, the variation of under test gas concentration can be measured by the variation for measuring porous silicon resistor or conductance.
There are following technical problems for 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 is the basis of human survival and development.Future, solar power generation will be as the main energy sources forms of human society.At present,
Solar cell mainly in the form of silicon solar cell, dye-sensitized solar cells and organic solar batteries, wherein, market
The silicon solar cell that upper major part is monocrystalline and polysilicon is representative, although it is high, performance stabilization excellent with transformation efficiency
Point, but when preparing silicon solar cell, refining high-purity silicon material needs to expend mass energy.
Under sunlight irradiation, dye molecule absorbs luminous energy, excitation state is excited to by eigenstate, due to excitation state
Unstable, excitation state electrons are 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 from external circuit to electrode, under the effect of the catalyst, by I in electrolyte3-It is reduced to I-, so cycle.
Based on this, the operation principle of device of the present invention is：Dye-sensitized solar cells and gas sensor, digital independent
Block coupled in series.Under sunlight, dye molecule absorbs luminous energy in dye-sensitized solar cells, is excited, the electronics of release
External circuit is flowed to by light anode, is formed into a loop by porous silicon-base gas sensor, data detection module, to electrode, warp
The catalytic action of carbon nanotubes is crossed, goes back I in original electrolyte3-Ion is thusly-formed working cycles；For gas sensor, in quilt
Under detection gas environment, porous silicon and tungsten oxide meeting adsorption gas molecule cause its electrical conductivity to change, and then act on electricity
The variation of stream, at this time data monitoring module can detect variation, finally show the gas concentration in real time.
The present invention provides a kind of outdoor safety socket with highly sensitive identification function, the outer surface peace of the safety socket
Detection device is filled, the detection device is based on self energizing sensing element, which includes dye sensitization of solar
Battery module and gas sensor module；Dye sensitization of solar module can as the working power of gas sensor module,
The effect of self energizing is generated to it, and then can realize the quick detection to pernicious gas in safety socket working environment, it is sensitive
Degree is high, and repeatability is high, while achievees the purpose that efficiently to utilize solar energy.
Further explanation is made to the present invention with reference to legend：
Fig. 1 is safety socket schematic diagram of the present invention.Detection device 2 is installed on the outer surface of safety socket 1.
Fig. 2 is the structure diagram 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 structure diagram of the gas identification module of the present invention.
Wherein：The stainless steel bases of 10-, 11- silicon chip substrates, 13- dye sensitization solar cell modules, 20- conductive catalytics
Layer, 21- Porous Silicon areas, 23- gas sensor modules, 30- electrolyte, 31-Au electrodes, 32- tungsten oxide nanos, 33- numbers
According to read module, 40-ITO electro-conductive glass substrates, 43- frames, 50- is to carbon nanotubes on electrode, 53- air admission holes, 60-TiO2Grain
Sublayer and dye molecules, 70- gas identification modules, 71- outer housings, 72- gas detection means, 73- diffusion control film layers,
74- indicates support powder, 75- glass tubes.
The invention will be further described with the following Examples.
Embodiment 1
A kind of outdoor safety socket with highly sensitive identification function that the embodiment of the present invention is provided, the safety socket
Outer surface installation detecting device, the detection device is based on self energizing sensing element, and further includes data read module
With gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；Institute
Stating dye sensitization solar cell module includes to electrode, light anode and is filled in the electricity between electrode and light anode
Solve liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at the conductive catalytic layer
On carbon nanotubes, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and
Dye molecules, the TiO2The grain size of particle about 450nm,；The gas sensor module includes silicon chip substrate, tungsten oxide is received
Rice noodles and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface vapor deposition of the Porous Silicon area has
Tungsten oxide layer film is with porous silicon together as the composite sensitive material of detection gas；The dye sensitization solar cell module
The aluminum that the specification that being arranged at surface with gas sensor module has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm
Cuboid framework in, the dye sensitization solar cell module by adhesive bonding to the outer surface of the frame, and
Make light anode upward, the gas sensor module, data read module are arranged at the lower portion, and the dye sensitization is too
Positive energy battery module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 carbon nanotubes；
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 being sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:It 3 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
Test data：
In obtained device, dye-sensitized solar cells is about 20 μm to the length of carbon nanotubes on electrode, gas
The aperture of porous silicon about 20~60nm in sensor；During test, which is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentration 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 obtains, the optimal transformation efficiency about 11.6% of dye-sensitized solar cells, and test is sent out after repeating 2000 times
Existing, dye-sensitized solar cells transformation efficiency drops to 9.3%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, selectivity and sensitivity to gas are put up the best performance, wherein, to NO2The detection limit of gas is 5ppm, to 100ppm
NO2, sensitivity 72, response time 7s；To NH3The detection limit of gas is 5ppm, to the NH of 100ppm3, sensitivity reaches
56, response time 14s.
Embodiment 2：
A kind of outdoor safety socket with highly sensitive identification function that the embodiment of the present invention is provided, the safety socket
Outer surface installation detecting device, the detection device is based on self energizing sensing element, and further includes data read module
With gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；Institute
Stating dye sensitization solar cell module includes to electrode, light anode and is filled in the electricity between electrode and light anode
Solve liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at the conductive catalytic layer
On carbon nanotubes, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and
Dye molecules, the TiO2The grain size of particle about 380nm；The gas sensor module includes silicon chip substrate, tungsten oxide is received
Rice noodles and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface vapor deposition of the Porous Silicon area has
Tungsten oxide layer film is with porous silicon together as the composite sensitive material of detection gas；The dye sensitization solar cell module
The aluminum that the specification that being arranged at surface with gas sensor module has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm
Cuboid framework in, the dye sensitization solar cell module by adhesive bonding to the outer surface of the frame, and
Make light anode upward, the gas sensor module, data read module are arranged at the lower portion, and the dye sensitization is too
Positive energy battery module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 7nm；3. CVD method is utilized,
CH4For carbon source, Ni is catalyst, grows carbon nanotubes；
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 being sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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 30 μm of cavity between the two, edge utilizes insulator
Encapsulation, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:It 3 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 40mA/cm2, etching time 2h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
Test data：
In obtained device, dye-sensitized solar cells is about 7 μm to the length of carbon nanotubes on electrode, and gas passes
The aperture of porous silicon about 5~25nm in sensor；During test, which is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentration 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 obtains, the optimal transformation efficiency about 11.2% of dye-sensitized solar cells, and test is sent out after repeating 2000 times
Existing, dye-sensitized solar cells transformation efficiency drops to 8.1%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, selectivity and sensitivity to gas are put up the best performance, wherein, to NO2The detection limit of gas is 12ppm, right
The NO of 100ppm2, sensitivity 52, response time 9s；To NH3The detection limit of gas is 9ppm, to the NH of 100ppm3, it is sensitive
Degree is up to 50, response time 6s.
Embodiment 3
A kind of outdoor safety socket with highly sensitive identification function that the embodiment of the present invention is provided, the safety socket
Outer surface installation detecting device, the detection device is based on self energizing sensing element, and further includes data read module
With gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；Institute
Stating dye sensitization solar cell module includes to electrode, light anode and is filled in the electricity between electrode and light anode
Solve liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at the conductive catalytic layer
On carbon nanotubes, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and
Dye molecules, the TiO2The grain size of particle about 550nm；The gas sensor module includes silicon chip substrate, tungsten oxide is received
Rice noodles and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface vapor deposition of the Porous Silicon area has
Tungsten oxide layer film is with porous silicon together as the composite sensitive material of detection gas；The dye sensitization solar cell module
The aluminum that the specification that being arranged at surface with gas sensor module has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm
Cuboid framework in, the dye sensitization solar cell module by adhesive bonding to the outer surface of the frame, and
Make light anode upward, the gas sensor module, data read module are arranged at the lower portion, and the dye sensitization is too
Positive energy battery module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 260nm, and the thickness of the Ni films is 15nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows carbon nanotubes；
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 being sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.2M 4- and 0.3M 1- propyl -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, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:It 5 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 20mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
Test data：
In obtained device, dye-sensitized solar cells is about 9 μm to the length of carbon nanotubes on electrode, and gas passes
The aperture of porous silicon about 5~50nm in sensor；During test, which is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentration 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 obtains, the optimal transformation efficiency about 10.3% of dye-sensitized solar cells, and test is sent out after repeating 2000 times
Existing, dye-sensitized solar cells transformation efficiency drops to 7.7%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, selectivity and sensitivity to gas are put up the best performance, wherein, to NO2The detection limit of gas is 16ppm, right
The NO of 100ppm2, sensitivity 51, response time 21s；To NH3The detection limit of gas is 13ppm, to the NH of 100ppm3, spirit
Sensitivity is up to 29, response time 17s.
Embodiment 4
A kind of outdoor safety socket with highly sensitive identification function that the embodiment of the present invention is provided, the safety socket
Outer surface installation detecting device, the detection device is based on self energizing sensing element, and further includes data read module
With gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；Institute
Stating dye sensitization solar cell module includes to electrode, light anode and is filled in the electricity between electrode and light anode
Solve liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at the conductive catalytic layer
On carbon nanotubes, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and
Dye molecules, the TiO2The grain size of particle about 800nm；The gas sensor module includes silicon chip substrate, tungsten oxide is received
Rice noodles and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface vapor deposition of the Porous Silicon area has
Tungsten oxide layer film is with porous silicon together as the composite sensitive material of detection gas；The dye sensitization solar cell module
The aluminum that the specification that being arranged at surface with gas sensor module has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm
Cuboid framework in, the dye sensitization solar cell module by adhesive bonding to the outer surface of the frame, and
Make light anode upward, the gas sensor module, data read module are arranged at the lower portion, and the dye sensitization is too
Positive energy battery module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 carbon nanotubes；
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 being sufficiently mixed, butyl titanate 5ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 6ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:It 3 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 48mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
Test data：
In obtained device, dye-sensitized solar cells is about 8 μm to the length of carbon nanotubes on electrode, and gas passes
The aperture of porous silicon about 20~40nm in sensor；During test, which is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentration 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 obtains, the optimal transformation efficiency about 8.7% of dye-sensitized solar cells, and test is sent out after repeating 2000 times
Existing, dye-sensitized solar cells transformation efficiency drops to 7.4%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, selectivity and sensitivity to gas are put up the best performance, wherein, to NO2The detection limit of gas is 26ppm, right
The NO of 100ppm2, sensitivity 39, response time 15s；To NH3The detection limit of gas is 12ppm, to the NH of 100ppm3, spirit
Sensitivity is up to 37, response time 9s.
Embodiment 5
A kind of outdoor safety socket with highly sensitive identification function that the embodiment of the present invention is provided, the safety socket
Outer surface installation detecting device, the detection device is based on self energizing sensing element, and further includes data read module
With gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；Institute
Stating dye sensitization solar cell module includes to electrode, light anode and is filled in the electricity between electrode and light anode
Solve liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at the conductive catalytic layer
On carbon nanotubes, the light anode include ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and
Dye molecules, the TiO2The grain size of particle about 300nm；The gas sensor module includes silicon chip substrate, tungsten oxide is received
Rice noodles and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface vapor deposition of the Porous Silicon area has
Tungsten oxide layer film is with porous silicon together as the composite sensitive material of detection gas；The dye sensitization solar cell module
The aluminum that the specification that being arranged at surface with gas sensor module has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm
Cuboid framework in, the dye sensitization solar cell module by adhesive bonding to the outer surface of the frame, and
Make light anode upward, the gas sensor module, data read module are arranged at the lower portion, and the dye sensitization is too
Positive energy battery module, the gas sensor module are connected with data read module by conducting wire.
Preferably, the making of the dye sensitization solar cell module includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 carbon nanotubes；
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 being sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds in absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethyl alcohol, 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrates of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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, injects 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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate to be rinsed well with deionized water, places into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:It 3 hydrofluoric acid (40%) and goes
The mixed liquor of ionized water, corrosion current 25mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
The Porous Silicon area of 1cm；
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
Then silicon chip substrate is put into tube furnace by 200nm, seal and be passed through nitrogen under normal pressure, utilizes 450 DEG C of growth tungsten oxides of CVD method
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 200nm.
The data read module is sent to the controller being arranged inside the detection device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module, the gas identification module
It is connected by conducting wire with the data read module, the gas identification module mainly connects by outer housing and with outer housing detachable
The gas detection means connect are formed, and the gas detection means are made 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 for use；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activation and carry
Body, it is stirring while adding, until being uniformly mixed, until supernatant liquor is less.After spontaneously drying in air, it is fitted into closed container
For use；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification for ID2.0mm ×
OD4.0mm), several 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 for use；
S4：The preparation of diffusion control film：Film is controlled as diffusion using the polyester film of 0.5mm thickness, after polymer PET drying,
The circular membrane for being 2.0mm into outer diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film one side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
Test data：
In obtained device, dye-sensitized solar cells is about 9 μm to the length of carbon nanotubes on electrode, and gas passes
The aperture of porous silicon about 30~70nm in sensor；During test, which is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentration 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 obtains, the optimal transformation efficiency about 11.7% of dye-sensitized solar cells, and test is sent out after repeating 4000 times
Existing, dye-sensitized solar cells transformation efficiency drops to 9.7%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, selectivity and sensitivity to gas are put up the best performance, wherein, to NO2The detection limit of gas is 14ppm, right
The NO of 100ppm2, sensitivity 67, response time 15s；To NH3The detection limit of gas is 30ppm, to the NH of 100ppm3, 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 in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Work as understanding, technical scheme can be modified or replaced equivalently, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (1)
1. a kind of outdoor safety socket with highly sensitive identification function, it is characterised in that：The outer surface of the safety socket
Installation detecting device, the detection device are based on self energizing sensing element, and further include data read module and gas identification mould
Block；The self energizing sensing element includes dye sensitization solar cell module (13) and gas sensor module (23)；The dye
Material sensitization solar battery module (13) includes to electrode, light anode and is filled in the electricity between electrode and light anode
Liquid (30) is solved, it is described to include stainless steel base (10), the conductive catalytic layer (20) close to stainless steel base (10), setting to electrode
Carbon nanotubes (50) on the conductive catalytic layer (20), the light anode include ITO electro-conductive glass substrate (40) and are located at
TiO in ITO electro-conductive glass substrate (40)2Particle and dye molecules (60), the TiO2The grain size 450nm of particle is described right
The length of carbon nanotubes (50) is 20 μm on electrode；The gas sensor module (23) includes silicon chip substrate (11), tungsten oxide
Nano wire (32) and Au electrodes (31), on the surface of the silicon chip substrate (11) corrosion have Porous Silicon area (21), it is described porous
The surface vapor deposition of silicon area has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas, described porous
The aperture of silicon is 20~60nm；The gas sensor module (23), which is arranged at surface, the air admission hole of an a diameter of 0.5cm
(53) specification is the dye sensitization solar cell module in the cuboid framework (43) of the aluminum of 5cm × 5cm × 1cm
(13) by adhesive bonding to the outer surface of the frame (43), and light anode is made upward, the gas sensor module
(23), data read module (33) is arranged at the frame (43) inside, the dye sensitization solar cell module (13), institute
Gas sensor module (23) is stated to connect by conducting wire with data read module (33)；
The making of the dye sensitization solar cell module (13) includes the following steps：
S1：It it is prepared by electrode：1. selecting the stainless steel base (10) that the specification that thickness is 0.3mm is 5cm × 5cm, thrown with sand paper
Light is cleaned by ultrasonic successively by acetone, ethyl alcohol, 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 method, CH4For carbon source, Ni is catalyst, grows carbon nanotubes；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it fully in 50 DEG C of stirred in water bath
Mixing adds in butyl titanate 9ml in mixed solution, and 1h is stirred in continuation in a water bath, absolute ethyl alcohol 10ml is then added in, in water
1h is stirred in bath, 12h is stood, obtains TiO2Solution is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Particle,
10ml ethyl alcohol, the mixing of 2ml acetylacetone,2,4-pentanediones are put into mortar and grind abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
TiO2The specification of slurry blade coating after cleaning is in the ITO electro-conductive glass substrate (40) of 5cm × 5cm, by being handled at 110 DEG C
Then 2h is immersed in the ethanol solution of N719 6h to get 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 -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 solution and is cleaned by ultrasonic 40min, cleaning solution is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；It takes out silicon chip substrate (11) to be rinsed well with deionized water, places into hydrofluoric acid
Middle immersion 10min, then it is cleaned by ultrasonic 20min respectively with acetone, ethyl alcohol, 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, in silicon chip substrate (11) surface formation size 1.5cm × 1cm
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 method
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 device by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection device
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is also set up there are one gas identification module (70), the gas identification module
(70) connected by conducting wire and the data read module (33), the gas identification module (70) mainly by outer housing (71) and
The gas detection means (72) being detachably connected with outer housing (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 for use, wherein, the specification of silica-gel carrier is 90~100 mesh；
S2：Indicate the preparation of carrier：It measures a certain amount of original liquid to be put into a container, pours into a certain amount of activated carrier, side
Edged stirs, until being uniformly mixed, until supernatant liquor is less, after spontaneously drying in air, is fitted into closed container for use；
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 several 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 for use；
S4：The preparation of diffusion control film：Using the polyester film of 0.5mm thickness as diffusion control film, after polymer PET drying, mould is used
Tool strikes out the circular membrane that outer diameter is 2.0mm；
S5：The assembling of gas identification module：The one side of control film adhesive bonding to glass tube will be spread, then weighed certain
Amount instruction support powder is slowly packed into glass tube to glass tube tight, and another side diffusion control film is bonded after smooth.
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Citations (4)
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|---|---|---|---|---|
| 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 |
| 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 |
| CN103661176A (en) * | 2012-08-31 | 2014-03-26 | 陕西浩瀚数码科技有限公司 | Automotive intelligent temperature control system |
| JP2015152519A (en) * | 2014-02-18 | 2015-08-24 | 株式会社Ｓｃｒｅｅｎホールディングス | Inspection device and inspection method |
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2016
- 2016-01-13 CN CN201610020716.7A patent/CN105680250B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103661176A (en) * | 2012-08-31 | 2014-03-26 | 陕西浩瀚数码科技有限公司 | Automotive intelligent temperature control system |
| JP2015152519A (en) * | 2014-02-18 | 2015-08-24 | 株式会社Ｓｃｒｅｅｎホールディングス | Inspection device and inspection method |
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