CN102354608B - Dye sensitized solar cell by utilizing complex film with carbon nanotubes and polymers as counter electrode - Google Patents
Dye sensitized solar cell by utilizing complex film with carbon nanotubes and polymers as counter electrode Download PDFInfo
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- 239000004408 titanium dioxide Substances 0.000 claims description 7
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- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 claims description 3
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 claims description 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
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Abstract
The invention, which belongs to the solar cell technology field, relates to a preparation method for a dye sensitized solar cell based on utilization of a complex film with carbon nanotubes and polymers as a vertical alignment counter electrode. According to the method, a pervasive method is employed; a monomer of a polymer is penetrated into an array; and then heating and curing processing is carried out to form a complex material; at last, a slicer is used to cut a sample into slices so as to obtain a complex film with carbon nanotubes and polymers. With regard to the film, the carbon nanotubes are vertical to film surfaces and are distributed uniformly, so that the upper and the lower surfaces of the film have good electrical conductivities. Moreover, there are lots of openings of carbon nanotube ends on the film surfaces, so that it is convenient to carry out applications including modification or catalyzation and the like. In addition, the complex film is used to replace platinumas a counter electrode and then a dye sensitized solar cell is constructed; and a good effect is realized, so that costs are substantially reduced. Therefore, the invention develops a series of solarcells that take alignment carbon nanotubes as electrodes.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of DSSC.
Background technology
The discovery of carbon nano-tube is a milestone on the World Science history.Japanese Iijima found carbon nano-tube (Carbon Nanotubes in 1991, CNTs) since [1], carbon nano-tube with its distinctive high stretch strong degree centigrade, high resiliency, from metal to semi-conductive electrology characteristic, high current load amount and high heat conductor and unique accurate one dimension tracheary element structure, in following high-tech area, have many potential using values, become the focus that people pay close attention to.
1994 [2] such as Ajayan with CNTs as inorganic filler join prepare polymer-CNT composite material in the polymeric matrix since, people have carried out a large amount of research work.General carbon nano-tube is considered to short fiber in filled polymer, and its distribution and orientation are arbitrarily.Its big L/D ratio and specific area make that model ylid bloom action power significantly strengthens between its pipe, cause easy gathering, twine bunchy or group [3], form defective and stress concentration point and make the decline of material mechanical performance in polymeric matrix, and reduce the functionalization effect.Along with the further investigation of carbon nano pipe array (ACNT), the macro length of nano-tube array has enough made single carbon pipe run through whole material in composite material.Utilize the order preparation of carbon nano pipe array to be uniformly dispersed, the polymer-carbon nanotube composite that anisotropy has specific functionality becomes new research focus.The method for preparing at present the polymer-carbon nanotube array composite material mainly contains two kinds of in-situ polymerization and polymer infiltration methods.Situ aggregation method, thermosetting polymer prepolymer or thermoplastic polymer monomer form polymer-ACNT composite material because molecular weight is less, and good fluidity than being easier to infiltrate the ACNT space, passes through in-situ polymerization again.The polymer infiltration method, some are relative with the ACNT compatibility better, molten condition or the less polymer of solution medium viscosity also again heating and melting or in solvent, disperse after, by the method for infiltration, immerse array inside, behind cooling curing or the solvent flashing, form composite material.
Equally, carbon nano-tube is widely used in making up organic solar batteries [4-13] efficiently, such as, carbon nano-tube is used to substitute the reduction that platinum comes the catalysis teriodide in DSSC, while also can be scattered in carbon nano-tube and promote electron diffusion [14] in the titania slurry, also can be scattered in transmission and the catalytic effect [15] that electrolyte gathers to promote electronics to carbon nano-tube.Be spin-coated on the FTO glass surface after having seminar that carbon nano-tube is disperseed, form electrode, obtain good effect [16]; There is seminar to pass through dispersing Nano carbon tubes, and uses ink-jet printing process to form electrode, also obtain good efficient [17].But because the random dispersion of carbon nano-tube has reduced separation and the transmission of electric charge, in order further to improve based on the efficient of carbon nano-tube to the organic solar batteries of electrode, urgent need to obtain having orientation carbon nanotube film to electrode, thereby and then improve the performance of battery.And height-oriented carbon nano-tube film is because its significant machinery and electric property [18-25] by research extensively and profoundly, at room temperature have 10 such as it
2The conductivity of S/cm, therefore based on orientation carbon nanotube film, we have prepared high efficiency, cheaply DSSC.
At present, the research of polymer-carbon nanotube array mainly concentrates on fields such as high performance structures material and photoelectric device.How to expand its range of application, improve the direction that the functionalization effect has become its development.
Summary of the invention
The object of the present invention is to provide a kind of efficient height, DSSC that cost is low.
DSSC provided by the invention, be in DSSC with carbon nano-tube/polymer laminated film platinum as electrode is obtained.
Among the present invention, the carbon nano-tube/polymer laminated film to electrode as DSSC, wherein carbon nano-tube is perpendicular to film surface, and evenly distribute, make the upper and lower surface of film have good conductivity, and film surface has a large amount of carbon nano-tube distal opening, is convenient to modify or other application such as catalysis.The present invention replaces platinum as electrode is made up DSSC with this kind film, and transformation efficiency is improved, and cost reduces.
The present invention also proposes the DSSC preparation method, and concrete steps are as follows:
(1) to the preparation of electrode, drip solvent at the FTO glass baseplate surface with the carbon nano-tube/polymer laminated film, after waiting to vapor away, closely link together by Van der Waals force between laminated film and the FTO glass, and 120-200 degree centigrade of down annealing, obtain at last containing the carbon nano-tube/polymer laminated film to electrode.
(2) preparation of work electrode, nano-crystalline titanium dioxide layer in FTO use silk screen print method printing on glass last layer 4-15 micron thickness, the nano-crystalline titanium dioxide layer efficient that experimental results show that 10 micron thickness is best, then 450-550 degree centigrade of calcining 25--35 minute and annealing down.When dropping to 25-150 degree centigrade Deng the work electrode temperature, they are transferred in the N719 dye solution of 0.5mM/L and soak, it is best to be transferred in the dye solution efficient when experimental results show that 120 degrees centigrade, after 12--18 hour, takes out and has adsorbed the work electrode of a large amount of dyestuffs and clean with acetonitrile.
(3) last work electrode and electrode encapsulated by an annular substrate, encapsulation pressure is 0.1-0.5MPa, and temperature is 110-140 degree centigrade, and electrolyte is by to injecting in the aperture on the electrode.Use miniature cover glass and substrate to seal aperture at last, obtain complete battery.
Among the present invention, the preparation method of the vertical orientated carbon nano-tube/polymer laminated film of carbon nano-tube is: at first, obtain carbon nano pipe array by chemical vapour deposition technique, carbon nano-tube has the orientation of height in the array; Then, adopt osmosis, make polymer monomer infiltrate carbon nano pipe array inside, formation composite material again is heating and curing; At last, section obtains the carbon nano-tube/polymer laminated film to sample by slicing machine.
Be example with the embedded carbon nano-tube of epoxy resin below, introduce the concrete operations step of carbon nano-tube/polymer laminated film preparation:
The first, the preparation of embedding stoste
On " EPON 812 " of classics prescription basis, increase DT-2 type flexibilizer; The method of preparation is: at first, configuration solution A and solution B: solution A by epoxy resin and dodecenylsuccinic acid acid anhydride by volume the ratio of 62:100 form, solution B is made up of epoxy resin and 100: 89 by volume ratio of methyl carbic anhydride; The A liquid for preparing and B liquid in ultrasonic cleaning machine the inside ultrasonic 10-30 minute make it even dispersion;
Then solution A and solution B are mixed with the volume ratio of 2:8, the flexibilizer that adds solution A and solution B cumulative volume 10% then, 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol that adds solution A and solution B cumulative volume at last, ultrasonic 10-30 minute, fully mix, obtain embedding stoste;
The second, the infiltration of epoxy resin
At first, join reagent 1, reagent 2, reagent 3 and reagent 4, reagent 1 is according to acetone: the volume ratio preparation of embedding stoste=10:1 to 2:1, reagent 2 is according to acetone: the volume ratio preparation of embedding stoste=2:1 to 1:2, reagent 3 is according to acetone: the volume ratio preparation of embedding stoste=1:2 to 1:10, and reagent 4 is pure embedding stoste; Then, carbon nano pipe array is immersed in the reagent 1, soaked 3-24 hour, be transferred to again in the reagent 2, soaked 3-24 hour, then be transferred in the reagent 3, soaked 3-24 hour, be transferred at last in the reagent 4, soaked 12-36 hour;
The 3rd, embedding is solidified
Sample after soaking in reagent 4 is put into suitable mould, injects embedding stoste then, in the polymerization case under the normal pressure 40-100 degree centigrade solidified 10-100 hour, namely obtain the carbon nano pipe array with the epoxy resin embedding;
The 4th, the embedding sample is cut into slices
Embedded sample is cut into slices with slicing machine, obtain the carbon nano-tube/polymer laminated film, the thickness range of composite membrane is 50 nanometers to 50 micron.
The carbon nano pipe array that uses in the described carbon nano-tube/polymer laminated film adopts the routine techniques preparation, and concrete steps are:
The catalyst structure of synthesizing carbon nanotubes array is Si/SiO
2/ Al
2O
3/ Fe, wherein, SiO
2Thickness is 300-1000 μ m, Al
2O
3Thickness is 10-30 nm, and Fe thickness is 0.5-1.5 nm, Al
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they are respectively by the film preparation of electron beam evaporation deposition instrument at silicon chip deposition one deck nano thickness; Adopt chemical vapour deposition technique, do carbon source with ethene, with argon gas and hydrogen as carrier gas, at the carbon nano pipe array that the synthetic high degree centigrade orientation of oxide layer Si substrate is being arranged; The therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, growth 5-20 min in tube furnace.
Fig. 7 is the sem photograph in carbon nano pipe array cross section, and wherein the diameter of multi-walled carbon nano-tubes is between the 7-12 nanometer, as shown in Figure 8.Fig. 1 a has illustrated the schematic diagram of carbon nano-tube/polymer composite array, and the carbon nano-tube/polymer laminated film is to obtain by using typical microtome or ultramicrotome to cut into slices.The thickness of laminated film can accurately be regulated, and can obtain from 1 micron to up to a hundred microns laminated film by typical microtome, by ultramicrotome, can obtain tens nanometers to the laminated film of hundreds of nanometer.The size of laminated film depends on the size of embedding array, and the height-oriented property of carbon nano-tube is not destroyed in the composite array, and this method is all available for single wall and multi-walled carbon nano-tubes, mainly studies with multi-walled carbon nano-tubes and resin here.
Vertical orientated carbon nano-tube/resin compounded the film that obtains is being transparent below 5 microns, but begins to become opaque greater than 5 microns, and these laminated films have good flexibility, can be repeatedly crooked, curl, and be not destroyed after the modification such as bending.Be the laminated film of 40 micron thickness among Fig. 2 a, and Fig. 2 b is the laminated film after curling.We have also further studied the internal structure of laminated film simultaneously, and Fig. 2 c and d are respectively the sem photographs of top and the side of laminated film.We can see that through the film that obtains after the section, the mouth of pipe all cuts off, and inner carbon nano-tube is still being arranged height-orientedly.The density of carbon nano-tube also can be regulated and control by changing synthetic parameters.Among the present invention, the density of carbon nano-tube is 10 in the film
11Root/cm
2
Stereoscan photograph has also illustrated simultaneously good compatibility between carbon nano-tube and the resin, carbon nano-tube is very accurately cut off and is not drawn out.Because the height-oriented property of carbon nano-tube in the laminated film, carbon nano-tube shows very outstanding electrical properties, and the resistivity of vertical orientated carbon nano-tube direction is 10
-4Cm, and surface resistivity is 10
-2Cm.Particularly importantly, laminated film electric property in the process of crooked deformation does not have to change substantially.Fig. 3 is the variation of laminated film bending angle from 0 degree to 180 degrees centigrade electric property.In addition, because laminated film has the transparency below 5 microns, use so can be used as flexible electrode at photoelectric field.For example it can replace the platinum electrode of DSSC, if below 5 microns, can replace ITO and be applied to organic solar batteries.
The basic principle of DSSC is as follows: under illumination, dye molecule absorbs solar energy, and its electron transition is to excitation state; Excitation state electronics instability, electronics transits to the Ti0 than low-lying level very soon
2Conduction band, this moment, dyestuff was oxidized; Be injected into Ti0
2The electronics of conduction band is enriched on the conductive substrates, and flows to external circuit to electrode (orientation carbon nanotube film) by conducting film, produces electric current; Dye molecule is in oxidation state, obtains electronics and revert to going back ortho states (ground state) and being regenerated from electrolyte; Electrolyte I
3-By from Ti0
2Conduction band, by electrode enter external circuit, the electron reduction that finally arrives negative electrode becomes I
-So just finished a circulation.This excites. oxidation. and the carrying out that the regeneration cycle of reduction is gone round and begun again just obtained the photoelectric current that continues.
Utilize laminated film to replace tradition among the present invention just the platinum in the electrode is made up novel DSSC.Picture 1b has showed the concrete structure of this new dye sensitization solar battery.The titanium dioxide layer that FTO silk screen printing last layer on glass is 10 microns covers the laminated film conduct to electrode as work electrode on the FTO., encapsulate by Surlyn at last as dyestuff with N719, inject electrolyte then, and the encapsulation hole.The battery that laminated film is made has good performance, because the carbon nano-tube end of opening can be than the more effective catalysis I that gets of carbon nanotube side-wall
3-Reduction.
Fig. 4 is the JV curve that the vertical orientated carbon nano-tube/polymer laminated film conduct of different-thickness records under a sunlight the constructed DSSC of electrode.Along with the reduction of slice thickness, open circuit voltage does not have to change substantially, and short circuit current and filling shadow are in continuous increase.
In order further to understand short circuit current and fill factor, curve factor cause of increased, we have tested the electrochemical impedance spectroscopy of battery under a sunlight, from Fig. 6, see, first semicircle at high-frequency region reduces along with reducing of laminated film thickness, and first semicircle reflects that just electronics is to the transmission resistance on electrode and the electrolyte interface, reducing of it caused filling the raising of shadow and short circuit current.
Fig. 5 d is the electricity conversion of the battery of different-thickness laminated film preparation, clearly, efficient increases along with the reduction of film thickness, battery is 10 microns situation at film thickness now, efficient can arrive 2.77%, and efficient can further improve by the thickness that reduces film, and we can also improve the density of carbon nano-tube simultaneously, the degree of orientation, methods such as the compatibility of carbon nano-tube and polymer and other polymer of selection are raised the efficiency.
Description of drawings
Fig. 1, a is the schematic diagram of the vertical orientated carbon nano-tube/polymer laminated film of preparation, b is for using the laminated film structural representation of DSSC afterwards.
Fig. 2, a and b are respectively the tiling figure of vertical orientated carbon nano-tube/polymer laminated film and the figure that curls, and c is the sem photograph at laminated film top, and d is the side cross-sectional views of laminated film.
After Fig. 3 is the bending of vertical orientated carbon nano-tube/polymer laminated film process different angles, the variation of electric property.
Fig. 4 is the JV curve that the vertical orientated carbon nano-tube/polymer laminated film conduct of different-thickness records under a sunlight the constructed DSSC of electrode.
Fig. 5, the vertical orientated carbon nano-tube/polymer laminated film of different-thickness is as the constructed DSSC of electrode is recorded various parameters under a sunlight variation.A is open circuit voltage, and b is short circuit current, and c is fill factor, curve factor, and d is electricity conversion.
Fig. 6, the vertical orientated carbon nano-tube/polymer laminated film of different-thickness is as the constructed DSSC of electrode is recorded electrochemical impedance spectroscopy under a sunlight.
Fig. 7, the ESEM sectional view of height-oriented carbon nano pipe array.
Fig. 8, the transmission electron microscope picture of single-root carbon nano-tube.
Embodiment
1, synthetic [26] of aligned carbon nanotube array.
Orthotropic carbon nano pipe array is with Fe (1nm)/Al
2O
3(10nm)/SiO
2/ Si uses typical chemical vapour deposition technique to synthesize in the quartz ampoule of tube furnace as catalyst.Al in the catalyst
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, they respectively by the electron beam evaporation deposition instrument in the film preparation of silicon chip deposition one deck nanometer thickness degree centigrade.Adopt chemical vapour deposition technique, do carbon source with ethene, argon gas and hydrogen are as carrier gas, at the carbon nano pipe array that the synthetic high degree centigrade orientation of oxide layer Si substrate is arranged.The self assembly of carbon pipe can be with reference to existing bibliographical information in synthetic details and the fiber.
2, the method for laminated film.
The first, the preparation of embedding stoste
On " EPON 812 " of classics prescription basis, increased DT-2 type flexibilizer; The method of preparation is: at first, configuration solution A and solution B: A liquid by epoxy resin and dodecenylsuccinic acid acid anhydride by volume the ratio of 62:100 form, B liquid is made up of epoxy resin and 100: 89 by volume ratio of methyl carbic anhydride; The A liquid for preparing and B liquid in ultrasonic cleaning machine the inside ultrasonic 10-30 minute make it even dispersion;
Then A liquid and B liquid are mixed with the volume ratio of 2:8, the flexibilizer that adds A liquid and B liquid cumulative volume 10% then adds 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol of cumulative volume, ultrasonic 10-30 minute at last, fully mix, obtain embedding stoste;
The second, the infiltration of epoxy resin
At first, join reagent 1, reagent 2, reagent 3 and reagent 4, reagent 1 is according to acetone: the volume ratio preparation of embedding stoste=10:1 to 2:1, reagent 2 is according to acetone: the volume ratio preparation of embedding stoste=2:1 to 1:2, reagent 3 is according to acetone: the volume ratio preparation of embedding stoste=1:2 to 1:10, and reagent 4 is pure embedding stoste; Then, carbon nano pipe array is immersed in the reagent 1, soaked 3-24 hour, be transferred to again in the reagent 2, soaked 3-24 hour, then be transferred in the reagent 3, soaked 3-24 hour, be transferred at last in the reagent 4, soaked 12-36 hour;
The 3rd, embedding is solidified
Sample after soaking in reagent 4 is put into suitable mould, injects embedding stoste then, in the polymerization case under the normal pressure 40-100 degree centigrade solidified 10-100 hour, can obtain with the embedded carbon nano pipe array of epoxy resin;
The 4th, the embedding sample is cut into slices
Embedded sample is cut into slices with slicing machine, obtain the carbon nano-tube/polymer laminated film, the thickness range of composite membrane is 50 nanometers to 50 micron.
3, to the preparation of electrode.
After obtaining laminated film, be to drip solvent at the FTO glass baseplate surface with carbon nano-tube film then, after waiting to vapor away, closely link together by Van der Waals force between laminated film and the FTO glass, and 120-200 degree centigrade of down annealing, obtain at last containing the carbon nano-tube/polymer laminated film to electrode.
4, the assembling of DSSC.
The work electrode of battery is the nano-crystalline titanium dioxide layer in FTO use silk screen print method printing on glass last layer 10 micron thickness, then 500 degrees centigrade of calcining 30 minutes and annealing down.Then at the TiCl of titanium dioxide surface with 50 mM/L
4The aqueous solution was handled 30 minutes down at 70 degrees centigrade, and 450 degrees centigrade of calcinings also annealing in 30 minutes in air then is optimized the titanium dioxide layer surface topography.When dropping to 120 degrees centigrade Deng the work electrode temperature, they are transferred in the N719 dye solution of 0.5mM/L and soak, after 16 hours, take out and adsorbed the work electrode of a large amount of dyestuffs and clean with acetonitrile.
Last work electrode and electrode encapsulated by an annular substrate, encapsulation pressure is 0.2MPa, and temperature is 125 degrees centigrade, and electrolyte is by to injecting in the aperture on the electrode.Use miniature cover glass and substrate to seal aperture at last, obtain complete battery.
The structure of carbon nano-tube is by transmitted electron Electronic Speculum (TEM, JEOL JEM-2100F operated at 200 kV) characterize, the structure of carbon nano-tube/polymer laminated film is to characterize by scanning electron microscopy (SEM, Hitachi FE-SEM S-4800 operated at 1 kV).The J-V curve of solar cell is by recording under a sun light intensity, and used solar simulator is the Oriel-94023 type, has Keithley 2400 sources table and 1000WXe lamp.The ac impedance spectroscopy of battery is by CHI 660a(Chinese Shanghai under a sunlight) the type electrochemical workstation records.Raman spectrum is to record at Renishaw inVia Reflex instrument, and excitation wavelength is 514.5 nm, and the energy of laser is 20 mW under the room temperature.The light transmittance of laminated film is to record at Shimadz UV-3150.
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Claims (3)
1. one kind is preparation method to the DSSC of electrode with the carbon nano-tube/polymer composite membrane, in the described DSSC, with the carbon nano-tube/polymer laminated film as to electrode; Carbon nano-tube is perpendicular to film surface in the described carbon nano-tube/polymer laminated film, and evenly distributes, and film surface has a large amount of carbon nano-tube distal opening; It is characterized in that the concrete steps that prepare are as follows:
(1) preparation is to electrode, drip solvent at the FTO glass baseplate surface with the carbon nano-tube/polymer laminated film, after waiting to vapor away, closely link together by Van der Waals force between laminated film and the FTO glass, and 120-200 degree centigrade of down annealing, obtain containing the carbon nano-tube/polymer laminated film to electrode;
(2) preparation work electrode is at the nano-crystalline titanium dioxide layer of FTO use silk screen print method printing on glass last layer 4-15 micron thickness, then 450-550 degree centigrade of calcining 25--35 minute and annealing down; When equitemperature drops to 25-150 degree centigrade, it is transferred in the N719 dye solution of 0.5mM/L soaked 12--18 hour, take out, obtained adsorbing the work electrode of a large amount of dyestuffs, and cleaned with acetonitrile;
(3) encapsulate by an annular substrate with work electrode with to electrode at last, encapsulation pressure is 0.1-0.5MPa, and temperature is 110-140 degree centigrade, by the aperture on the electrode is injected electrolyte; Use miniature cover glass and substrate to seal aperture then, obtain complete battery;
Wherein, the preparation process of carbon nano-tube/polymer laminated film is:
The first, the preparation of embedding stoste
On " EPON 812 " prescription basis, increase DT-2 type flexibilizer; The method of preparation is:
At first, configuration solution A and solution B: solution A by epoxy resin and dodecenylsuccinic acid acid anhydride by volume the ratio of 62:100 form, solution B is made up of epoxy resin and 100: 89 by volume ratio of methyl carbic anhydride; The A liquid for preparing and B liquid in ultrasonic cleaning machine the inside ultrasonic 10-30 minute make it even dispersion;
Then, solution A and solution B are mixed with the volume ratio of 2:8, the flexibilizer that adds solution A and solution B cumulative volume 10%, 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol that adds solution A and solution B cumulative volume at last, ultrasonic 10-30 minute, fully mix, obtain embedding stoste;
The second, the infiltration of epoxy resin
At first, join reagent 1, reagent 2, reagent 3 and reagent 4, reagent 1 is according to acetone: the volume ratio preparation of embedding stoste=10:1 to 2:1, reagent 2 is according to acetone: the volume ratio preparation of embedding stoste=2:1 to 1:2, reagent 3 is according to acetone: the volume ratio preparation of embedding stoste=1:2 to 1:10, and reagent 4 is pure embedding stoste; Then, carbon nano pipe array is immersed in the reagent 1, soaked 3-24 hour, be transferred to again in the reagent 2, soaked 3-24 hour, then be transferred in the reagent 3, soaked 3-24 hour, be transferred at last in the reagent 4, soaked 12-36 hour;
The 3rd, embedding is solidified
Sample after soaking in reagent 4 is put into suitable mould, injects embedding stoste then, in the polymerization case under the normal pressure 40-100 degree centigrade solidified 10-100 hour, namely obtain the carbon nano pipe array with the epoxy resin embedding;
The 4th, the embedding sample is cut into slices
Embedded sample is cut into slices with slicing machine, obtain the carbon nano-tube/polymer laminated film, the thickness range of composite membrane is 50 nanometers to 50 micron.
2. the preparation method of DSSC according to claim 1 is characterized in that the preparation process of the carbon nano pipe array in the carbon nano-tube/polymer composite membrane is:
The catalyst structure of synthesizing carbon nanotubes array is Si/SiO
2/ Al
2O
3/ Fe, wherein, SiO
2Thickness is 300-1000 μ m, Al
2O
3Thickness is 10-30 nm, and Fe thickness is 0.5-1.5 nm, Al
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they are respectively by the film of electron beam evaporation deposition instrument at silicon chip deposition one deck nano thickness; Adopt chemical vapour deposition technique, do carbon source with ethene, as carrier gas, having oxide layer Si substrate to synthesize height-oriented carbon nano pipe array with argon gas and hydrogen; The therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, growth 5-20 min in tube furnace.
3. being prepared by claim 1 described preparation method, is DSSC to electrode with the carbon nano-tube/polymer composite membrane.
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