CN105551803B - A kind of outdoor gas boiler based on self energizing detection - Google Patents
A kind of outdoor gas boiler based on self energizing detection Download PDFInfo
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- CN105551803B CN105551803B CN201610021667.9A CN201610021667A CN105551803B CN 105551803 B CN105551803 B CN 105551803B CN 201610021667 A CN201610021667 A CN 201610021667A CN 105551803 B CN105551803 B CN 105551803B
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- 239000007789 gas Substances 0.000 claims description 215
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- 229910052782 aluminium Inorganic materials 0.000 claims description 7
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical class [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
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Classifications
-
- 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 gas boiler based on self energizing detection, by the way that in gas fired-boiler outer surface installation detecting device, the detection means is based on self energizing sensing element, and also includes data read module and gas identification module；Self energizing sensing element includes dye sensitization solar cell module and gas sensor module, working power of the dye sensitization solar cell module as gas sensor module, produce the effect of self energizing, the quick detection to pernicious gas in gas fired-boiler working environment can be realized, high sensitivity, repeatability are high.
Description
Technical field
The present invention relates to field of boilers, is more particularly to a kind of outdoor gas boiler based on self energizing detection.
Background technology
Gas fired-boiler includes gas hot water boiler, gas-fired water heating boiler, gas-steam boiler etc., wherein gas-fired water heating boiler
Also referred to as gas heating boiler and combustion gas bath boiler, gas fired-boiler refer to the boiler that fuel is combustion gas, gas-fired boiler as its name suggests
Stove and oil burning boiler, electric boiler are most economical by comparison, thus most of people all have selected gas fired-boiler as steam, adopt
The warm, boiler plant of bathing.
However, because existing gas fired-boiler application is wide, when it is in different operating environment, it is proposed
New requirement functionally, such as the detection function to hazardous gas.
The content of the invention
A kind of family based on self energizing detection is provided it is an object of the invention to avoid weak point of the prior art
Outer gas fired-boiler.
The purpose of the present invention is achieved through the following technical solutions：
A kind of outdoor gas boiler based on self energizing detection, the outer surface installation detecting device of the gas fired-boiler, institute
State detection means and be based on self energizing sensing element, the self energizing sensing element includes dye sensitization solar cell module and gas
Sensor assembly；Dye sensitization of solar module can produce self energizing as the working power of gas sensor module to it
Effect, and then the quick detection to pernicious gas in gas fired-boiler working environment can be realized, high sensitivity, and repeatability
Height, while reach the purpose for efficiently utilizing solar energy.
The dye sensitization solar cell module includes to electrode, light anode and is filled in described to electrode and light sun
Electrolyte between pole, it is described electrode is included stainless steel base, close to stainless steel base conductive catalytic layer, be arranged at it is described
CNT on conductive catalytic layer, the light anode include ITO electro-conductive glass substrate and in ITO electro-conductive glass substrates
TiO2Particle and dye molecules, the TiO2The particle diameter of particle about 145nm, the length to CNT on electrode are 7 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 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 10~90nm；The dye sensitization solar cell module and gas pass
Sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum cuboid
In framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light anode by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the DSSC
Module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl
Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator
Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
The present invention is advantageous in that：
(1) present invention is based on DSSC technology and gas sensor technology, designs the gas of self energizing
Sensor, i.e., the energy of working sensor is provided with DSSC；By DSSC with it is porous
Silicon substrate gas sensor is connected, including solar module, sensor assembly, data read module and gas detection module；
Solar cell is used as the working power of sensor by solar power generation, and the effect of self energizing is produced to gas sensor,
Solar energy resources has been maximally utilized, has reduced energy waste and environmental pollution.
(2) in DSSC in electrode, generally use Pt is used as to electrode catalyst agent material, still
Platinum is a kind of noble metal, expensive, and the present invention substitutes Pt as catalyst using CNT, makes simple, catalytic efficiency
Height, it is cheap；Prepare cost to substantially reduce, be advantageous to widely popularize application；In addition, gas sensor module is adopted in the present invention
It is sensitive material with porous silicon, while tungsten oxide layer film, porous silica material and tungsten oxide material knot is deposited in porous silicon surface
Cooperate as composite sensitive material, can in quick environment-identification gas situation of change, high sensitivity is convenient and swift.
(3) present invention is provided with a gas identification module that can identify gas type behind data read module,
The instruction support powder used in the gas detection means set in the module quickly judges gas type, when its work is run
Dye sensitization solar cell module is not needed to provide energy, overall save has saved the energy, and realizes passive detection row
Deflation body；It is efficient and convenient.
Brief description of the drawings
Invention is described further using accompanying drawing, but the embodiment in accompanying drawing does not form any limitation of the invention,
For one of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to the following drawings
Its accompanying drawing.
Fig. 1 is the schematic diagram of gas fired-boiler of the present invention.
Fig. 2 is the structural representation of the dye sensitization solar cell module of the present invention.
Fig. 3 is the gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of the gas sensor module of the present invention.
Fig. 5 is the dye sensitization solar cell module of the present invention and the combination schematic diagram of gas sensor module.
Fig. 6 is the structural representation of the gas identification module of the present invention.
Embodiment
In general, after gas component of the sensing element in gas sensor in extraneous test environment changes,
Its physical quantity being measured accordingly can also change, and gas sensor detects the specific gas componant to change
Come, and then converted the change of the electric signal of reflection gas componant change, such as resistance, electric capacity, dielectric etc..
Porous silicon is a kind of material with open structure, and it can be oxidized by monocrystalline silicon or polysilicon in hydrofluoric acid
To be made.Porous silicon has the advantages that good optical property, huge surface area, and at present, porous silicon is to humidity, You Jiqi
Body, NOX、COX、O2, HCl etc. show detection property.Gas sensor using porous silicon as sensitive material, mainly inhaled using it
The change of electrical conductivity carrys out detection gas after attached gas.When porous silicon is placed in detected gas environment, gas can be in porous silicon
Suction-operated occurs for surface, and gas molecule can capture hole or electronics from porous silicon surface, cause the resistance of porous silicon to become
Change, the change by measuring porous silicon resistor or conductance can measure the change of under test gas concentration.
Following technical problem be present in the gas sensor in presently relevant technology：Gas sensor at work, it is necessary to
External power supply or battery drive its work, largely can cause environmental pollution and energy waste using battery, have to environment latent
Harm, therefore, it is necessary to seek a kind of new gas sensor of environmental protection and energy saving.Solar energy is as a kind of sustainable new
The energy, it is the basis of human survival and development.In future, solar power generation is by as the main energy sources form of human society.At present,
Solar cell mainly in the form of silicon solar cell, DSSC and organic solar batteries, wherein, market
The silicon solar cell that upper major part is monocrystalline and polysilicon is representative, although it has transformation efficiency high, stable performance excellent
Point, but when preparing silicon solar cell, refining high-purity silicon material needs to expend mass energy.
Under sunshine irradiation, dye molecule absorbs luminous energy, and it is excited to excitation state by eigenstate, due to excitation state
Unstable, its excitation state electrons is transferred to the conductive layer that Nanometer Semiconductor Films pass through light anode from dye molecule, and then
To external circuit；The dye molecule for losing electronics can be by I in neighbouring electrolyte-Revert to eigenstate, and I-Ion is oxidized to
I3-, electronics is transferred to electrode from external circuit, in the presence of catalyst, by I in electrolyte3-It is reduced to I-, so circulation.
Based on this, the operation principle of device of the present invention is：DSSC and gas sensor, digital independent
Block coupled in series.Under sunlight, dye molecule absorbs luminous energy in DSSC, is excited, the electronics of release
External circuit is flowed to by light anode, loop is formed by porous silicon-base gas sensor, data detection module, to electrode, warp
The catalytic action of CNT is crossed, goes back I in original electrolyte3-Ion, it is thusly-formed working cycles；For gas sensor, in quilt
Under detection gas environment, porous silicon and tungsten oxide meeting adsorption gas molecule, its electrical conductivity is caused to change, and then act on electricity
The change of stream, now data monitoring module can detect change, finally show the gas concentration in real time.
The present invention provides a kind of outdoor gas boiler based on self energizing detection, the outer surface installation inspection of the gas fired-boiler
Device is surveyed, the detection means is based on self energizing sensing element, and the self energizing sensing element includes DSSC
Module and gas sensor module；Dye sensitization of solar module can be as the working power of gas sensor module, to it
The effect of self energizing is produced, and then the quick detection to pernicious gas in gas fired-boiler working environment can be realized, high sensitivity,
And it is repeated high, while reach the purpose for efficiently utilizing solar energy.
Further explanation is made to the present invention with reference to legend：
Fig. 1 is gas fired-boiler schematic diagram of the present invention.Detection means 2 is installed on the outer surface of gas fired-boiler 1.
Fig. 2 is the structural representation of the dye sensitization solar cell module of the present invention.
Fig. 3 is the gas sensor module schematic top plan view of the present invention.
Fig. 4 is the sectional view of the gas sensor module of the present invention.
Fig. 5 is the dye sensitization solar cell module of the present invention and the combination schematic diagram of gas sensor module.
Fig. 6 is the structural representation of the gas identification module of the present invention.
Wherein：The stainless steel bases of 10-, 11- silicon chip substrates, 12- silicon chip substrates, 13- dye sensitization solar cell modules,
20- conductive catalytic layers, 21- Porous Silicon areas, 23- gas sensor modules, 30- electrolyte, 31-Au electrodes, 32- tungsten oxides are received
Rice noodles, 33- data read modules, 40-ITO electro-conductive glass substrates, 43- frameworks, 50- is to CNT on electrode, 53- air inlets
Hole, 60-TiO2Particle layer and dye molecules, 70- gas identification modules, 71- shell bodies, 72- gas detection means, 73- expand
Dissipate control film layer, 74- instruction support powders, 75- glass tubes.
The invention will be further described with the following Examples.
Embodiment 1
A kind of outdoor gas boiler based on self energizing detection that embodiments of the invention are provided, the gas fired-boiler it is outer
Portion surface installation detecting device, the detection means are based on self energizing sensing element, and it is gentle also to include data read module
Body identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dye
Material sensitization solar battery module includes to electrode, light anode and is filled in the electrolysis between electrode and light anode
Liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged on the conductive catalytic layer
CNT, the light anode includes ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dye
Expect molecular layer, the TiO2The particle diameter of particle about 145nm,；The gas sensor module includes silicon chip substrate, tungsten oxide nanometer
Line and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one
Composite sensitive material of the layer oxidation tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and
The specification that gas sensor module is arranged at surface and has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm aluminum
In cuboid framework, the dye sensitization solar cell module, to the outer surface of the framework, and is made by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization sun to light anode
Energy battery module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 500nm, and the thickness of the Ni films is 10nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl
Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator
Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 45mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 7 μm, and gas passes
The aperture of porous silicon about 10~90nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant
Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 11.6% of DSSC, and test is sent out after repeating 2000 times
Existing, DSSC 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 100ppm NH3, sensitivity reaches
56, response time 4s.
Embodiment 2：
A kind of outdoor gas boiler based on self energizing detection that embodiments of the invention are provided, the gas fired-boiler it is outer
Portion surface installation detecting device, the detection means are based on self energizing sensing element, and it is gentle also to include data read module
Body identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dye
Material sensitization solar battery module includes to electrode, light anode and is filled in the electrolysis between electrode and light anode
Liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged on the conductive catalytic layer
CNT, the light anode includes ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dye
Expect molecular layer, the TiO2The particle diameter of particle about 38nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano
With Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer
Aoxidize composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module is gentle
Body sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum length
In cube framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization of solar to anode
Battery module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 7nm；3. CVD is utilized,
CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl
Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 30 μm of cavity between the two, edge utilizes insulator
Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:3 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 40mA/cm2, etching time 2h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 60nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 7 μm, and gas passes
The aperture of porous silicon about 5~25nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant
Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 10.2% of DSSC, and test is sent out after repeating 2000 times
Existing, DSSC transformation efficiency drops to 8.1%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 12ppm, right
100ppm NO2, sensitivity 52, response time 9s；To NH3The detection limit of gas is 9ppm, to 100ppm NH3, it is sensitive
Degree is up to 50, response time 6s.
Embodiment 3
A kind of outdoor gas boiler based on self energizing detection that embodiments of the invention are provided, the gas fired-boiler it is outer
Portion surface installation detecting device, the detection means are based on self energizing sensing element, and it is gentle also to include data read module
Body identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dye
Material sensitization solar battery module includes to electrode, light anode and is filled in the electrolysis between electrode and light anode
Liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged on the conductive catalytic layer
CNT, the light anode includes ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dye
Expect molecular layer, the TiO2The particle diameter of particle about 55nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano
With Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer
Aoxidize composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module is gentle
Body sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum length
In cube framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization of solar to anode
Battery module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 260nm, and the thickness of the Ni films is 15nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.2M 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, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:5 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 20mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 9 μm, and gas passes
The aperture of porous silicon about 5~50nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant
Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 10.3% of DSSC, and test is sent out after repeating 2000 times
Existing, DSSC 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
100ppm NO2, sensitivity 51, response time 21s；To NH3The detection limit of gas is 13ppm, to 100ppm NH3, spirit
Sensitivity is up to 29, response time 17s.
Embodiment 4
A kind of outdoor gas boiler based on self energizing detection that embodiments of the invention are provided, the gas fired-boiler it is outer
Portion surface installation detecting device, the detection means are based on self energizing sensing element, and it is gentle also to include data read module
Body identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dye
Material sensitization solar battery module includes to electrode, light anode and is filled in the electrolysis between electrode and light anode
Liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged on the conductive catalytic layer
CNT, the light anode includes ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dye
Expect molecular layer, the TiO2The particle diameter of particle about 80nm；The gas sensor module includes silicon chip substrate, tungsten oxide nano
With Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one layer
Aoxidize composite sensitive material of the tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module is gentle
Body sensor module be arranged at surface have an a diameter of 0.5cm air admission hole specification be 5cm × 5cm × 1cm aluminum length
In cube framework, the dye sensitization solar cell module, to the outer surface of the framework, and makes light by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization of solar to anode
Battery module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 350nm, and the thickness of the Ni films is 15nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 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, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 6ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl
Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator
Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 2:3 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 48mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 70nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 8 μm, and gas passes
The aperture of porous silicon about 20~40nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant
Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 8.7% of DSSC, and test is sent out after repeating 2000 times
Existing, DSSC transformation efficiency drops to 7.4%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 26ppm, right
100ppm NO2, sensitivity 39, response time 15s；To NH3The detection limit of gas is 12ppm, to 100ppm NH3, spirit
Sensitivity is up to 37, response time 9s.
Embodiment 5
A kind of outdoor gas boiler based on self energizing detection that embodiments of the invention are provided, the gas fired-boiler it is outer
Portion surface installation detecting device, the detection means are based on self energizing sensing element, and it is gentle also to include data read module
Body identification module；The self energizing sensing element includes dye sensitization solar cell module and gas sensor module；The dye
Material sensitization solar battery module includes to electrode, light anode and is filled in the electrolysis between electrode and light anode
Liquid, it is described to electrode include stainless steel base, close to stainless steel base conductive catalytic layer, be arranged on the conductive catalytic layer
CNT, the light anode includes ITO electro-conductive glass substrate and the TiO in ITO electro-conductive glass substrates2Particle and dye
Expect molecular layer, the TiO2The particle diameter of particle about 100nm；The gas sensor module includes silicon chip substrate, tungsten oxide nanometer
Line and Au electrodes, on the surface of the silicon chip substrate corrosion have Porous Silicon area, the surface evaporation of the Porous Silicon area has one
Composite sensitive material of the layer oxidation tungsten film with porous silicon together as detection gas；The dye sensitization solar cell module and
The specification that gas sensor module is arranged at surface and has the air admission hole of an a diameter of 0.5cm is 5cm × 5cm × 1cm aluminum
In cuboid framework, the dye sensitization solar cell module, to the outer surface of the framework, and is made by adhesive bonding
Upward, the gas sensor module, data read module are arranged at the lower portion, the dye sensitization sun to light anode
Energy battery module, the gas sensor module are connected with data read module by wire.
Preferably, the making of the dye sensitization solar cell module comprises the following steps：
S1：It is prepared by electrode：1. the stainless steel base that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper
Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；2. metal Cr is plated in stainless steel base using magnetron sputtering method
Film and Ni films form conductive catalytic layer, and the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；3. utilize CVD
Method, CH4For carbon source, Ni is catalyst, grows CNT；
S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make it in 50 DEG C of stirred in water bath
It is sufficiently mixed, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, then adds absolute ethyl alcohol 10ml,
1h is stirred in a water bath, is stood 12h, is obtained TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Grain
Son, the mixing of 10ml ethanol, 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. suitable in taking step 2.
The TiO of amount2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrates, by being handled at 110 DEG C
2h, 6h in N719 ethanol solution is then immersed in, produces light anode；
S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methyl
Iodonium imidazolide salts, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；
S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge utilizes insulator
Encapsulation, is injected the electrolyte into cavity, forms dye sensitization solar cell module；
The preparation of the gas sensor module comprises the following steps：
1. cutting silicon chip substrate size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio
For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate to be rinsed well with deionized water, place into hydrofluoric acid and soak
10min is steeped, then is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；
2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 hydrofluoric acid (40%) and go
The mixed liquor of ionized water, corrosion current 25mA/cm2, etching time 1h, formed on silicon chip substrate surface size 1.5cm ×
1cm Porous Silicon area；
3. silicon chip substrate is put into magnetic control sputtering device, one layer of tungsten film is deposited in its porous silicon region field surface, thickness is
200nm, then silicon chip substrate is put into tube furnace, seals and be passed through nitrogen under normal pressure, utilize 450 DEG C of growth tungsten oxides of CVD
Nano wire；
4. the Au electrodes of two round point shapes, the diameter of the Au electrodes are made on Porous Silicon area using magnetron sputtering method
For 1mm, thickness 100nm.
The data read module is sent to the controller being arranged inside the detection means by wireless communication module
Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means
Data value is transmitted to detection data basestation；
Further, the self energizing sensing element is additionally provided with a gas identification module, the gas identification module
Connected by wire with the data read module, the gas identification module mainly connects by shell body and with shell body detachable
The gas detection means connect are formed, and the gas detection means are made up of diffusion control film layer, instruction support powder and glass tube；
The preparation process of the gas detection means is as follows：
S1：The processing and activation of carrier：The silica-gel carrier sieved (90~100 mesh) is placed in 600 DEG C of Muffle furnaces
2h is calcined, after cooling, bottling is stand-by；
S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, is poured into a certain amount of activation and is carried
Body, it is stirring while adding, until it is well mixed, untill supernatant liquor is less.After spontaneously drying in atmosphere, it is fitted into closed container
It is stand-by；
S3：The preparation of glass tube：Select internal diameter is uniform, glass tube that transparency is good (specification be ID2.0mm ×
OD4.0mm), some sections of the glass tube that length is 30mm is intercepted into, with sand paper by both sides feather plucking, then successively with suds, clear
Water, distilled water are clean by glass tube cleaning, dry stand-by；
S4：The preparation of diffusion control film：Film is controlled as diffusion using polyester film thick 0.5mm, after polymer PET drying,
The circular membrane for being 2.0mm into external diameter with mould punching；
S5：The assembling of gas identification module：By the diffusion control film side of adhesive bonding to glass tube, then weigh
Certain amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
Test data：
In obtained device, the length to CNT on electrode of DSSC is about 9 μm, and gas passes
The aperture of porous silicon about 30~70nm in sensor；During test, the device is put into 1m3Light tight hermetical testing container, take
100mW/cm2Xenon source simulated solar irradiation, the NO of various concentrations is passed through into test container respectively2Gas.
The sensitivity of gas is represented with following formula：R%=(I0±It/I0) × 100%, in formula, in the feelings that light source power is constant
Under condition, I0Not to be passed through NO2When device in size of current, ItTo be passed through NO2Size of current when testing gas in device.
Test is obtained, the optimal transformation efficiency about 11.7% of DSSC, and test is sent out after repeating 2000 times
Existing, DSSC transformation efficiency drops to 9.7%, reproducible；When about 40 DEG C of gas sensor operating temperature
When, its selectivity and sensitivity to gas is put up the best performance, wherein, to NO2The detection limit of gas is 14ppm, right
100ppm NO2, sensitivity 67, response time 15s；To NH3The detection limit of gas is 25ppm, to 100ppm NH3, spirit
Sensitivity is up to 36, response time 23s.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (1)
- A kind of 1. outdoor gas boiler based on self energizing detection, it is characterised in that：The gas fired-boiler outer surface installation inspection Device is surveyed, the detection means is based on self energizing sensing element, and also includes data read module and gas identification module；Should be certainly Energy supply sensing element includes dye sensitization solar cell module (13) and gas sensor module (23)；The dye sensitization is too Positive energy battery module (13) includes to electrode, light anode and is filled in the electrolyte between electrode and light anode (30), it is described to electrode include stainless steel base (10), close to stainless steel base (10) conductive catalytic layer (20), be arranged at institute The CNT (50) on conductive catalytic layer (20) is stated, the light anode includes ITO electro-conductive glass substrate (40) and led positioned at ITO TiO on electric substrate of glass (40)2Particle and dye molecules (60), the TiO2The particle diameter 145nm of particle, it is described to electrode The length of upper CNT (50) is 7 μm；The gas sensor module (23) includes silicon chip substrate (11), tungsten oxide nano (32) and Au electrodes (31), corrosion has Porous Silicon area (21), the Porous Silicon area on the surface of the silicon chip substrate (11) Surface evaporation have tungsten oxide layer film and porous silicon together as the composite sensitive material of detection gas, the hole of the porous silicon Footpath is 10~90nm；The dye sensitization solar cell module (13) and gas sensor module (23) are arranged at surface and have one The specification of a diameter of 0.5cm air admission hole (53) is the dyestuff in the cuboid framework (43) of 5cm × 5cm × 1cm aluminum Outer surface of the sensitization solar battery module (13) by adhesive bonding to the framework (43), and make light anode upward, institute State gas sensor module (23), data read module (33) is arranged at the framework (43) inside, the dye sensitization sun Energy battery module (13), the gas sensor module (23) are connected with data read module (33) by wire；The making of the dye sensitization solar cell module (13) comprises the following steps：S1：It is prepared by electrode：1. the stainless steel base (10) that the specification for being 0.3mm from thickness is 5cm × 5cm, is thrown with sand paper Light, it is cleaned by ultrasonic successively by acetone, ethanol, deionized water；It is 2. gold-plated in stainless steel base (10) using magnetron sputtering method Belong to Cr films and Ni films form conductive catalytic layer (20), the thickness of the Cr films is 300nm, and the thickness of the Ni films is 15nm；③ Utilize CVD, CH4For carbon source, Ni is catalyst, grows CNT；S2：The preparation of light anode：1. taking absolute ethyl alcohol 50ml, ethylene glycol amine 2ml respectively, make its abundant in 50 DEG C of stirred in water bath Mixing, butyl titanate 9ml is added in mixed solution, 1h is stirred in continuation in a water bath, absolute ethyl alcohol 10ml is then added, in water 1h is stirred in bath, 12h is stood, obtains TiO2Solution, filtered, dried；2. take the TiO of 5g steps 1. middle drying2Particle, 10ml ethanol, the mixing of 2ml acetylacetone,2,4-pentanediones, it is put into mortar and grinds abundant, obtained TiO2Slurry；It is 3. appropriate in taking step 2. TiO2The specification of slurry blade coating after cleaning is in 5cm × 5cm ITO electro-conductive glass substrate (40), by being handled at 110 DEG C 2h, 6h in N719 ethanol solution is then immersed in, produces light anode；S3：Electrolyte quota：0.5M lithium iodides, 0.06M iodine, the tertiary yl pyridines of 0.1M 4- and 0.3M 1- propyl group -3- methylimidazoles Salt compounded of iodine, solvent are volume ratio 1:1 acetonitrile and propylene carbonate mixed liquor；S4：Assembling：Electrode will be covered in light anode, and form 50 μm of cavity between the two, edge is encapsulated using insulator, Electrolyte (30) is injected into cavity, forms dye sensitization solar cell module (13)；The preparation of the gas sensor module (23) comprises the following steps：1. cutting silicon chip substrate (11) size to 2cm × 2cm, it is put into cleaning fluid and is cleaned by ultrasonic 40min, cleaning fluid is volume ratio For 3:1 98% concentrated sulfuric acid and 40% hydrogen peroxide；Take out silicon chip substrate (11) to be rinsed well with deionized water, place into hydrofluoric acid Middle immersion 10min, then it is cleaned by ultrasonic 20min respectively with acetone, ethanol, deionized water successively；2. using electrochemical process corrosion of silicon, corrosive liquid is prepared, corrosive liquid is volume ratio 1:3 40% hydrofluoric acid and deionized water Mixed liquor, corrosion current 45mA/cm2, etching time 1h, size 1.5cm × 1cm is formed on silicon chip substrate (11) surface Porous Silicon area (21)；3. silicon chip substrate (11) is put into magnetic control sputtering device, one layer of tungsten film, thickness is deposited on its Porous Silicon area (21) surface For 200nm, then silicon chip substrate (11) is put into tube furnace, seals and is passed through nitrogen under normal pressure, utilizes 450 DEG C of growths of CVD Tungsten oxide nano；4. the Au electrodes (31) of two round point shapes, the Au electrodes are made on Porous Silicon area (21) using magnetron sputtering method (31) a diameter of 1mm, thickness 100nm；The data read module (33) is sent to the controller being arranged inside the detection means by wireless communication module Module, the controller module communicated by wireless communication module and GPRS module, and will be detected by the detection means Data value is transmitted to detection data basestation；Further, the self energizing sensing element is additionally provided with a gas identification module (70), the gas identification module (70) connected by wire and the data read module (33), the gas identification module (70) mainly by shell body (71) and The gas detection means (72) being detachably connected with shell body (71) are formed, and the gas detection means (72) control film by diffusion Layer (73), instruction support powder (74) and glass tube (75) are formed；The preparation process of the gas detection means (72) is as follows：S1：The processing and activation of carrier：The silica-gel carrier sieved is placed in 600 DEG C of Muffle furnaces and calcines 2h, after cooling, dress Bottle is stand-by, wherein, the size of silica-gel carrier is 90~100 mesh；S2：Indicate the preparation of carrier：The original liquid of measured amounts is put into a container, pours into a certain amount of activated carrier, side Edged stirs, until it is well mixed, untill supernatant liquor is less, after spontaneously drying in atmosphere, it is fitted into stand-by in closed container；S3：The preparation of glass tube：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 polyester film thick 0.5mm as diffusion control film, after polymer PET drying, mould is used Tool strikes out the circular membrane that external diameter is 2.0mm；S5：The assembling of gas identification module：The side of control film adhesive bonding to glass tube will be spread, then weighed certain Amount instruction support powder slowly loads in glass tube to glass tube tight, and opposite side diffusion control film is bonded after smooth.
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| JP2011187183A (en) * | 2010-03-04 | 2011-09-22 | Casio Computer Co Ltd | Dye-sensitized solar cell |
| CN102831753B (en) * | 2012-08-16 | 2015-10-28 | 上海霖睿自控设备有限公司 | Sun power gas detection alarm system |
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