CN105489386B - A kind of solar cell frame with quick detection gas - Google Patents

A kind of solar cell frame with quick detection gas Download PDF

Info

Publication number
CN105489386B
CN105489386B CN201610023645.6A CN201610023645A CN105489386B CN 105489386 B CN105489386 B CN 105489386B CN 201610023645 A CN201610023645 A CN 201610023645A CN 105489386 B CN105489386 B CN 105489386B
Authority
CN
China
Prior art keywords
module
gas
solar cell
glass tube
porous silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610023645.6A
Other languages
Chinese (zh)
Other versions
CN105489386A (en
Inventor
张新兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Huachang Aluminum Factory Co ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201610023645.6A priority Critical patent/CN105489386B/en
Publication of CN105489386A publication Critical patent/CN105489386A/en
Application granted granted Critical
Publication of CN105489386B publication Critical patent/CN105489386B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S30/00—Structural details of PV modules other than those related to light conversion
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

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

Abstract

The invention discloses a kind of solar cell frame with quick detection gas, by the way that in solar cell frame outer surface installation detecting device, 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, produce the effect of self energizing, it can realize the quick detection to pernicious gas in solar cell frame working environment, high sensitivity, repeatability are high.

Description

A kind of solar cell frame with quick detection gas
Technical field
The present invention relates to field of solar energy, is more particularly to a kind of solar-electricity pool side with quick detection gas Frame.
Background technology
Solar cell frame, also known as solar components frame, refer to the aluminium alloy type that solar cell panel assembly is formed Material fixed frame or stent.Its main function is fixed, seals solar cell module, extends its service life etc..
However, since the extensive use of solar cell is, it is necessary to which it adapts to different environment, such as the inspection to environmental gas Brake etc..
The content of the invention
It is an object of the invention to avoid shortcoming of the prior art and providing a kind of has quick detection gas work( The solar cell frame of energy.
The purpose of the present invention is achieved through the following technical solutions：
A kind of solar cell frame with quick detection gas, solar cell frame outer surface installation Detection device, the detection device are based on self energizing sensing element, which includes dye sensitization of solar electricity Pond module and gas sensor module；Dye sensitization of solar module can be right as the working power of gas sensor module It produces the effect of self energizing, and then can realize the quick inspection to pernicious gas in working environment residing for solar cell frame Survey, high sensitivity, and repeatability is 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 particle diameter of particle about 85nm, the length to carbon nanotubes on electrode are 9 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 10~30nm；The dye sensitization solar cell module and gas sensing Device module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid frame In frame, the dye sensitization solar cell module, to the outer surface of the frame, and makes light anode court by adhesive bonding On, the gas sensor module, data read module are arranged at the lower portion, the dye-sensitized solar cells mould Block, 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 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, 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 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 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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, 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；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 × 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
The invention has the beneficial effects that：
(1) present invention is based on dye-sensitized solar cells technology and gas sensor technology, designs the gas of self energizing Sensor, i.e., provide 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 produced 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 its work is run It is not required dye sensitization solar cell module 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 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, it can also be obtained according to the following drawings Its attached drawing.
Fig. 1 is the schematic diagram of solar cell frame 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.
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 change of the electric signal of reflection gas componant change, such as resistance, capacitance, dielectric etc..
Porous silicon is a kind of material with open structure, it can be aoxidized 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, is 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.
There are following technical problem 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.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, 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, 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, under the action 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：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 change of stream, at this time data monitoring module can detect change, finally show the gas concentration in real time.
The present invention provides a kind of solar cell frame with quick detection gas, outside the solar cell frame Portion surface installation detecting device, the detection device are based on self energizing sensing element, and it is quick which includes dyestuff Change solar module and gas sensor module；Dye sensitization of solar module can be as the work of gas sensor module Make power supply, the effect of self energizing is produced to it, and then can realize to being harmful to gas in working environment residing for solar cell frame The quick detection of body, high sensitivity, and repeatability is high, while achieve the purpose that efficiently to utilize solar energy.
Further explanation is made to the present invention with reference to legend：
Fig. 1 is solar cell frame schematic diagram of the present invention.Detection device 2 is installed on the outside of solar cell frame 1 Surface.
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, 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- frames, 50- is to carbon nanotubes 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 solar cell frame with quick detection gas that the embodiment of the present invention is provided, the sun The outer surface installation detecting device of energy battery frame, the detection device is based on self energizing sensing element, and further includes number According to read module and gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensing Device module；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 particle diameter of particle about 85nm,；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 table of the Porous Silicon area Face evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas；The dye sensitization of solar Battery module and gas sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification for 5cm × 5cm × In the cuboid framework of the aluminum of 1cm, the dye sensitization solar cell module passes through adhesive bonding to the frame Outer surface, and make light anode upward, the gas sensor module, data read module are arranged at the lower portion, described Dye sensitization solar cell 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 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, 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 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 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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, 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；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 × 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to carbon nanotubes on electrode of dye-sensitized solar cells is about 9 μm, and gas passes The aperture of porous silicon about 10~30nm in sensor；During test, which 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 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, its selectivity and sensitivity to gas is 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 4s.
Embodiment 2：
A kind of solar cell frame with quick detection gas that the embodiment of the present invention is provided, the sun The outer surface installation detecting device of energy battery frame, the detection device is based on self energizing sensing element, and further includes number According to read module and gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensing Device module；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 particle diameter of particle about 38nm；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 table of the Porous Silicon area Face evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas；The dye sensitization of solar Battery module and gas sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification for 5cm × 5cm × In the cuboid framework of the aluminum of 1cm, the dye sensitization solar cell module passes through adhesive bonding to the frame Outer surface, and make light anode upward, the gas sensor module, data read module are arranged at the lower portion, described Dye sensitization solar cell 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 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, 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 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 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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 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；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 × 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to carbon nanotubes on electrode of dye-sensitized solar cells is about 7 μm, 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 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 obtains, the optimal transformation efficiency about 10.2% 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, its selectivity and sensitivity to gas is 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 solar cell frame with quick detection gas that the embodiment of the present invention is provided, the sun The outer surface installation detecting device of energy battery frame, the detection device is based on self energizing sensing element, and further includes number According to read module and gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensing Device module；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 particle diameter of particle about 55nm；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 table of the Porous Silicon area Face evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas；The dye sensitization of solar Battery module and gas sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification for 5cm × 5cm × In the cuboid framework of the aluminum of 1cm, the dye sensitization solar cell module passes through adhesive bonding to the frame Outer surface, and make light anode upward, the gas sensor module, data read module are arranged at the lower portion, described Dye sensitization solar cell 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 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, 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 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 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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 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, 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；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 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to carbon nanotubes on electrode of dye-sensitized solar cells is about 9 μm, 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 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 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, its selectivity and sensitivity to gas is 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 solar cell frame with quick detection gas that the embodiment of the present invention is provided, the sun The outer surface installation detecting device of energy battery frame, the detection device is based on self energizing sensing element, and further includes number According to read module and gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensing Device module；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 particle diameter of particle about 80nm；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 table of the Porous Silicon area Face evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas；The dye sensitization of solar Battery module and gas sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification for 5cm × 5cm × In the cuboid framework of the aluminum of 1cm, the dye sensitization solar cell module passes through adhesive bonding to the frame Outer surface, and make light anode upward, the gas sensor module, data read module are arranged at the lower portion, described Dye sensitization solar cell 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 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, 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 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 is sufficiently mixed, butyl titanate 5ml 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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, 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；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 × 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to carbon nanotubes on electrode of dye-sensitized solar cells is about 8 μm, 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 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 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, its selectivity and sensitivity to gas is 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 solar cell frame with quick detection gas that the embodiment of the present invention is provided, the sun The outer surface installation detecting device of energy battery frame, the detection device is based on self energizing sensing element, and further includes number According to read module and gas identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensing Device module；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 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 table of the Porous Silicon area Face evaporation has composite sensitive material of the tungsten oxide layer film with porous silicon together as detection gas；The dye sensitization of solar Battery module and gas sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification for 5cm × 5cm × In the cuboid framework of the aluminum of 1cm, the dye sensitization solar cell module passes through adhesive bonding to the frame Outer surface, and make light anode upward, the gas sensor module, data read module are arranged at the lower portion, described Dye sensitization solar cell 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 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, 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 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 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Grain Son, the mixing of 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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, 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；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 × 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 Silicon chip substrate, is then put into tube furnace by 200nm, seals and is 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 additionally provided with a gas identification module, the gas identification module Connected by conducting 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 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：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activation and carry Body, it is stirring while adding, until being uniformly 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 for 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 the polyester film of 0.5mm thickness, after polymer PET drying, The circular membrane for being 2.0mm into outside 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 another side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to carbon nanotubes on electrode of dye-sensitized solar cells is about 9 μm, 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 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 obtains, the optimal transformation efficiency about 11.7% of dye-sensitized solar cells, and test is sent out after repeating 2000 times Existing, dye-sensitized solar cells 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 The NO of 100ppm2, sensitivity 67, response time 15s；To NH3The detection limit of gas is 25ppm, 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 with reference to preferred embodiment to the present invention, those of ordinary skill in the art should Work as understanding, can be to technical scheme technical scheme is 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 1. solar cell frame with quick detection gas, it is characterised in that：The solar cell frame Outer surface installation detecting device, which is based on self energizing sensing element, and it is gentle to further include data read module Body identification module；The self energizing sensing element includes dye sensitization solar cell module (13) and gas sensor module (23)；The dye sensitization solar cell module (13) includes to electrode, light anode and is filled in described to electrode and light Electrolyte (30) between anode, it is described that electrode is urged including stainless steel base (10), the conduction close to stainless steel base (10) Change layer (20), the carbon nanotubes (50) being arranged on the conductive catalytic layer (20), the light anode includes ITO electro-conductive glass bases Bottom (40) and the TiO in ITO electro-conductive glass substrate (40)2Particle and dye molecules (60), the TiO2The particle diameter of particle 85nm, the length to carbon nanotubes on electrode (50) are 9 μm；The gas sensor module (23) includes 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 evaporation of the Porous Silicon area has composite sensing of the tungsten oxide layer film with porous silicon together as detection gas Material, the aperture of the porous silicon is 10~30nm；The dye sensitization solar cell module (13) and gas sensor mould The specification that block (23) is arranged at surface and has the air admission hole (53) of an a diameter of 0.5cm is the rectangular of the aluminum of 5cm × 5cm × 1cm In body frame (43), appearance of the dye sensitization solar cell module (13) by adhesive bonding to the frame (43) Face, and make light anode upward, the gas sensor module (23), data read module (33) are arranged in the frame (43) Portion, the dye sensitization solar cell module (13), the gas sensor module (23) and data read module (33) are logical Cross conducting wire connection；
    The making of the dye sensitization solar cell module (13) includes the following steps：
    S1：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, 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 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 its abundant in 50 DEG C of stirred in water bath Mixing, adds butyl titanate 9ml in mixed solution, and 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, is filtered, dry；2. take the TiO of 5g steps 1. middle drying2Particle, 10ml ethanol, 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 2h, is then immersed in 6h in the ethanol solution of N719, up to 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 solution and is cleaned by ultrasonic 40min, cleaning solution 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 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 additionally provided with a 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 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 size of silica-gel carrier is 90~100 mesh；
    S2：Indicate the preparation of carrier：Measure a certain amount of original liquid to be put into a container, pour into a certain amount of activated carrier, side Edged stirs, until being uniformly mixed, untill supernatant liquor is less, after spontaneously drying in atmosphere, is fitted into stand-by in closed container；
    S3：The preparation of glass tube：The glass tube that internal diameter is uniform, transparency is good is selected, if intercepting into the glass tube that length is 30mm Dry section, it is then with suds, clear water, distilled water that glass tube cleaning is clean successively with sand paper by both sides feather plucking, dry it is stand-by, Wherein, glass pipe size is ID2.0mm × OD4.0mm；
    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 outside 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 another side diffusion control film is bonded after smooth.
CN201610023645.6A 2016-01-13 2016-01-13 A kind of solar cell frame with quick detection gas Active CN105489386B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610023645.6A CN105489386B (en) 2016-01-13 2016-01-13 A kind of solar cell frame with quick detection gas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610023645.6A CN105489386B (en) 2016-01-13 2016-01-13 A kind of solar cell frame with quick detection gas

Publications (2)

Publication Number Publication Date
CN105489386A CN105489386A (en) 2016-04-13
CN105489386B true CN105489386B (en) 2018-04-20

Family

ID=55676307

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610023645.6A Active CN105489386B (en) 2016-01-13 2016-01-13 A kind of solar cell frame with quick detection gas

Country Status (1)

Country Link
CN (1) CN105489386B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112485296B (en) * 2019-09-11 2022-04-05 中国科学院金属研究所 Preparation method of self-powered gas sensor based on single-walled carbon nanotube

Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN105489386A (en) 2016-04-13

Similar Documents

Publication Publication Date Title
CN105529191A (en) High-conversion-efficiency solar cell based vehicle license plate recognition device of parking lot
TW558842B (en) Solar cell
CN106525942A (en) Construction method of photoinduced electric sensor with time as read signal
CN105466973B (en) A kind of safety barrier with quick detection function
CN105489386B (en) A kind of solar cell frame with quick detection gas
CN105489385A (en) Electric vehicle charging station based on self-powering detecting function
CN105679545B (en) A kind of curtain based on fast gas identification function
CN105679537B (en) A kind of power operation door-plate based on the detection of self energizing gas
CN105466974B (en) A kind of high voltage power supply that can realize fast gas identification function
CN105429596B (en) A kind of product open air presentation device based on high efficiency solar cell
CN105486820B (en) A kind of outdoor video monitoring device with gas detection function
CN105680250B (en) A kind of outdoor safety socket with highly sensitive identification function
CN105673377A (en) Metering refueling pump based on high-efficiency solar cell
CN105529190B (en) A kind of parking lot banister with self energizing gas detection function
CN105466052B (en) A kind of solar water heater with high duplication detection function
CN105674603B (en) A kind of solar thermal collector with automatic gas detection function
CN105428077B (en) A kind of outdoor illumination equipment based on high efficiency solar cell
CN105551803B (en) A kind of outdoor gas boiler based on self energizing detection
CN105500608B (en) A kind of novel injection molding mould with highly sensitive detection function
CN105655137A (en) Outdoor communication device based on self-powered detection
CN105699436A (en) Exhaust gas detection device based on solar cell high in conversion rate
CN105674192A (en) Solar street lamp with high-sensitivity detecting function
CN106195885B (en) A kind of Solar lamp
CN105527322A (en) High-sensitivity self-energizing automobile exhaust gas detection device
CN105513810A (en) Oil tank with high-repetitiveness detection function of refueling station

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information

Inventor after: Zhang Xinxing

Inventor before: Xiao Baiyu

CB03 Change of inventor or designer information
TA01 Transfer of patent application right

Effective date of registration: 20180316

Address after: 362400 No. 19 South pit street, peach boat Township, Anxi County, Quanzhou, Fujian

Applicant after: Zhang Xinxing

Address before: Gulou road Zhenhai District 315200 Zhejiang city of Ningbo province No. 32

Applicant before: Xiao Baiyu

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20200814

Address after: 225300 Jiangsu city of Taizhou province Gaogang Branch Park Avenue on the north side of entrepreneurship

Patentee after: Taizhou jinzai Intellectual Property Service Co.,Ltd.

Address before: 362400 No. 19 South pit street, peach boat Township, Anxi County, Quanzhou, Fujian

Patentee before: Zhang Xinxing

TR01 Transfer of patent right
CP02 Change in the address of a patent holder

Address after: 225300 intellectual property rights of Tianjin University, north of Chuangye Avenue, Gaogang District, Taizhou City, Jiangsu Province

Patentee after: Taizhou jinzai Intellectual Property Service Co.,Ltd.

Address before: 225300 Jiangsu city of Taizhou province Gaogang Branch Park Avenue on the north side of entrepreneurship

Patentee before: Taizhou jinzai Intellectual Property Service Co.,Ltd.

CP02 Change in the address of a patent holder
TR01 Transfer of patent right

Effective date of registration: 20221121

Address after: 221600 east of Hanxing Road, Peixian Economic Development Zone, Xuzhou City, Jiangsu Province

Patentee after: JIANGSU HUACHANG ALUMINUM FACTORY Co.,Ltd.

Address before: 225300 intellectual property rights of Jinzhuan, north side of Chuangye Avenue, science and Innovation Park, Gaogang District, Taizhou City, Jiangsu Province

Patentee before: Taizhou jinzai Intellectual Property Service Co.,Ltd.

TR01 Transfer of patent right