CN105789456A - External wall composite board with energy conservation and environmental protection functions - Google Patents
External wall composite board with energy conservation and environmental protection functions Download PDFInfo
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- CN105789456A CN105789456A CN201610172369.XA CN201610172369A CN105789456A CN 105789456 A CN105789456 A CN 105789456A CN 201610172369 A CN201610172369 A CN 201610172369A CN 105789456 A CN105789456 A CN 105789456A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/30—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure
- E04C2/38—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure with attached ribs, flanges, or the like, e.g. framed panels
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/44—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the purpose
- E04C2/46—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the purpose specially adapted for making walls
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/44—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the purpose
- E04C2/52—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the purpose with special adaptations for auxiliary purposes, e.g. serving for locating conduits
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses an external wall composite board with energy conservation and environmental protection functions. The external surface of the external wall composite board is provided with a polymer solar cell module; the external wall composite board uses the polymer solar cell to generate electric energy, and the electric energy is supplied to a heating module; the polymer solar cell has a sandwich structure and is composed of an anode electrode, an organic active layer and a cathode electrode; the anode electrode comprises ITO glass, a WOX thin film, a WOX nanowire thin film and a PEDOT:PSS buffer layer sequentially from outside to inside; the organic active layer is located between the anode electrode and the cathode electrode; and the cathode electrode comprises a Ti sheet, an Al film and a TiO2 thin film sequentially from outside to inside. The polymer solar cell module can use solar energy to generate electric energy, the energy conversion efficiency is high, the stability is good, the cycle working time and the service life are long, and the purpose of effectively using the solar resources can be realized.
Description
Technical field
The present invention relates to composite plate field, be specifically related to the outer wall composite board of a kind of energy-saving environmental-protection function.
Background technology
Outer wall composite board is that one is arranged on external wall, plays the functional composite plate of the effects such as decoration, protection, insulation, and main material is timber, metal etc..
Existing outer wall composite board typically only has the functions such as decoration, insulation, and outer wall composite board local environment is generally outdoor, and sunlight resource is more sufficient.
Summary of the invention
It is an object of the invention to avoid the deficiencies in the prior art part to provide the outer wall composite board of a kind of energy-saving environmental-protection function.
The purpose of the present invention is achieved through the following technical solutions:
Providing the outer wall composite board of a kind of energy-saving environmental-protection function, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 500nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Compared with prior art beneficial effects of the present invention:
1. the method adopting magnetron sputtering is deposited with one layer of WO on ITO surfaceXThin film, it is formed with ito thin film to be good Ohmic contact, reduces contact berrier, improves ito anode and collect the ability in hole；
2. configuration aspects, introduces one layer of WO between ITO and PEDOT:PSS cushionXMembrane structure, itself and PEDOT:PSS cushion form double-deck hole transmission layer, and at WOXFilm surface growth has WOXNano wire film, this nano wire directly contacts with organic active layer, increases the contact area of electrode and organic active layer, and this structure substantially increases ito anode electrode to the collection efficiency in hole in organic active layer, creates beyond thought effect；
One layer of Al film of 3.Ti cathode electrode surface magnetic control, forms reflector layer, and adopts TiO between Al film and organic active layer2Modifying, it mates with active layer bandgap, it is possible to play the effect of electron transfer layer and hole blocking layer.
Accompanying drawing explanation
Utilize accompanying drawing that invention is described further, but the embodiment in accompanying drawing does not constitute any limitation of the invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the following drawings.
Fig. 1 is the polymer solar battery module diagram of the present invention.
Wherein: 01-ITO glass, 02-WOXThin film, 03-PEDOT:PSS cushion, 04-WOXNano wire film, 05-organic active layer, 06-TiO2Thin film, 07-Al film, 08-Ti sheet.
Detailed description of the invention
Entering 21 century, along with the development of science and technology, the energy has become as the up-to-date driving force of world development and economic growth, is the bases depended on for existence of the mankind.Due to the consumption of the non-regeneration energies such as oil, coal, natural gas, seeking with Renewable Energy Development is the main method solving current energy problem.And solar energy is a kind of cleaning, environmental protection, inexhaustible alternative energy source.At present, the solar energy come into operation includes two kinds, a kind of for utilizing the heat energy of solar energy, mainly having water heater, solar cooker etc., another kind is the luminous energy utilizing the sun, namely photovoltaic effect is utilized, converting light energy into electric energy, solaode is the important devices of solar energy photoelectric conversion, and it is the device directly converting the solar into electric energy, classify according to material therefor, it is possible to be divided into inorganic solar cell and organic solar batteries.Inorganic solar cell, based on silica-base material, has the advantages such as conversion efficiency height, good stability, and shortcoming is that material purity requires high, and complicated process of preparation is expensive etc.；Organic solar batteries can be divided into again organic molecule and polymer solar battery, its material source is extensive, preparation technology is simple, the method large area such as solution spin coating, silk screen printing can be adopted to prepare, therefore organic solar batteries has more the advantage of low cost, and the research of organic solar batteries has become as the emphasis of people's extensive concern.
Simple polymer solar battery structure is single layer structure, middle one layer is served as active layer for organic material, two ends are the electrode of different work functions, wherein a termination electrode is transparent, shining intermediate layer organic material through light, it can produce the exciton of bound state, owing to the combination of exciton can be generally 0.1～1.0eV, the built in field that two end electrodes produces is difficult to be separated into electron-hole pair, therefore introduces double-decker；Active layer in double-decker is made up of two kinds of organic materials, a kind of material serves as electron donor, another kind serves as electron acceptor, under light illumination, in material, electronics is stimulated, there is electron transfer in the interface of electron donor with electron acceptor, greatly improve the separation efficiency of exciton in organic material；Introduce again body heterojunction subsequently, body heterojunction be by electron donor together with electron acceptor blended, three dimension scale is formed hetero-junctions, electron donor and electron acceptor are beneficial to electron transfer being mixed with of nanoscale on the one hand, on the other hand electron donor enrichment phase and electron acceptor enrichment phase can form continuous phase, be beneficial to the electronics after separation, hole each mutually in be transferred to two end electrodes.
At present, in polymer solar cells, generally adopting ITO is transparent anode, it is used for collecting hole, Al thin film is as negative electrode, collect electronics, the ability of electric charge is collected owing to the contact berrier between electrode and active layer determines electrode, in order to enable hole better to collect, cushion is added between ITO and active layer, most widely used at present is PEDOT (3, the polymer of 4-ethylenedioxy thiophene monomer) and the mixed solution of PSS (poly styrene sulfonate), PEDOT is good conductive material, PSS PEDOT can be made better to disperse in the solution so as film forming and regulate film conductivity.
But, the ITO contacted, in acidity, can be brought corrosivity by PSS, and PEDOT:PSS also has very strong hygroscopicity, the performance of meeting strong influence device and life-span.
Inefficient, stability and life-span for existing polymer solar battery are poor, the problem such as the structure of cushion, technique, and the present invention by introducing WO between ITO and PEDOT:PSS cushionXThin film and WOXNano thread structure, itself and PEDOT:PSS cushion form double-deck hole transmission layer, adopt Ti sheet as cathode electrode simultaneously, and one layer of Al film of magnetic control in its surface, form reflector layer, substantially increase the absorption efficiency of sunlight, and between Al film and organic active layer, adopt TiO2Modifying, to the efficiency of this polymer solar battery, stability improves, life serves beyond thought effect.
Illustrate that the invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is the polymer solar battery module diagram of the present invention.
Wherein: 01-ITO glass, 02-WOXThin film, 03-PEDOT:PSS cushion, 04 WOXNano wire film, 05-organic active layer, 06-TiO2Thin film, 07-Al film, 08-Ti sheet.
The invention will be further described with the following Examples.
Embodiment 1:
As shown in Figure 1, the outer wall composite board of a kind of energy-saving environmental-protection function that embodiments of the invention provide, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 500nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 14.15mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.9%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value.
Test shows, the outer wall composite board of this invention to the energy conversion efficiency of sunlight up to 7.9%, it is possible to utilize the solar energy of outer wall composite board local environment efficiently, have good stability, and circulating working time, last a long time, be effectively utilized solar energy resources, be effectively saved electric energy.
Embodiment 2
The outer wall composite board of a kind of energy-saving environmental-protection function that embodiments of the invention provide, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 430nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 300W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 360r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 14.06mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.1%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 90% of initial value.
Test shows, the outer wall composite board of this invention to the energy conversion efficiency of sunlight up to 7.1%, it is possible to utilize the solar energy of outer wall composite board local environment efficiently, have good stability, and circulating working time, last a long time, be effectively utilized solar energy resources, be effectively saved electric energy.
Embodiment 3:
The outer wall composite board of a kind of energy-saving environmental-protection function, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 330nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 14.15mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.2%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value.
Test shows, the outer wall composite board of this invention to the energy conversion efficiency of sunlight up to 7.2%, it is possible to utilize the solar energy of outer wall composite board local environment efficiently, have good stability, and circulating working time, last a long time, be effectively utilized solar energy resources, be effectively saved electric energy.
Embodiment 4
The outer wall composite board of a kind of energy-saving environmental-protection function, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 430nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2500r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 13.63mA/cm2, open-circuit voltage is about 0.94V, and energy conversion efficiency (PCE) is up to 7.3%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value.
Test shows, the outer wall composite board of this invention to the energy conversion efficiency of sunlight up to 7.3%, it is possible to utilize the solar energy of outer wall composite board local environment efficiently, have good stability, and circulating working time, last a long time, be effectively utilized solar energy resources, be effectively saved electric energy.
Embodiment 5
The outer wall composite board of a kind of energy-saving environmental-protection function, this outer wall composite board utilizes polymer solar battery to produce electric energy, and this electric energy can be used to supply heating module work, and the building etc. inside External Wall composite plate plays insulation effect.
Described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 530nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06).
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 9.66mA/cm2, open-circuit voltage is about 0.92V, and energy conversion efficiency (PCE) is up to 7.4%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 81% of initial value.
Test shows, the outer wall composite board of this invention to the energy conversion efficiency of sunlight up to 7.4%, it is possible to utilize the solar energy of outer wall composite board local environment efficiently, have good stability, and circulating working time, last a long time, be effectively utilized solar energy resources, be effectively saved electric energy.
Finally should be noted that; above example is only in order to illustrate technical scheme; but not limiting the scope of the invention; although having made to explain to the present invention with reference to preferred embodiment; it will be understood by those within the art that; technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention.
Claims (2)
1. an outer wall composite board for energy-saving environmental-protection function, this outer wall composite board utilizes polymer solar battery to produce electric energy, it is characterised in that described outer wall composite board is made up of framework, polymer solar battery module, heating module；Ito glass one outward facing sides of described polymer solar battery module assembles, and described heating module is connected with polymer solar battery module by conducting electricity；Described polymer solar battery module is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass, WO from outside to insideXThin film, WOXNano wire film, PEDOT:PSS cushion, wherein, WOXNano wire film is grown on WOXOn thin film, PEDOT:PSS cushion is filled between nano thread structure, and nanowire length is more than PEDOT:PSS buffer layer thickness；Described organic active layer is between anode electrode and cathode electrode, and organic active layer thickness is 500nm；Described cathode electrode is followed successively by Ti sheet, Al film, TiO from outside to inside2Thin film.
2. outer wall composite board according to claim 1, it is characterised in that the preparation method of described polymer solar battery module is as follows:
Step one, cleans ITO substrate: taking the commercial ito glass of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film and WOXNano wire film: putting in magnetic control sputtering device by the ITO substrate after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXFilm surface obtains WOXNano wire film；
Step 3, spin coating PEDOT:PSS cushion: take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion solidify；
Step 4, prepares organic active layer: this programme organic active layer adopts PCDTBT/PC71BM, and weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparing solution, wherein the concentration of PCDTBT is 5mg/ml, solution is heated in 65 DEG C of water-baths and stirs, with abundant dissolving；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet, cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C.Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film, is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered in ITO substrate so that cathode electrode Al film one end and organic active layer end thereof contacts in ITO substrate,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C.
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| CN105359289A (en) * | 2013-07-31 | 2016-02-24 | 富士胶片株式会社 | Photoelectric conversion element and solar cell |
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| US20080176030A1 (en) * | 2002-06-08 | 2008-07-24 | Fonash Stephen J | Lateral collection photovoltaics |
| CN104081880A (en) * | 2012-02-07 | 2014-10-01 | 三井金属矿业株式会社 | Electrode foil and electronic device |
| CN105359289A (en) * | 2013-07-31 | 2016-02-24 | 富士胶片株式会社 | Photoelectric conversion element and solar cell |
| CN103606633A (en) * | 2013-11-28 | 2014-02-26 | 电子科技大学 | Organic electroluminescence and photovoltaic integration device and manufacturing method |
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