CN106935408A - Dye-sensitized solar cell anode and preparation method thereof - Google Patents
Dye-sensitized solar cell anode and preparation method thereof Download PDFInfo
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- CN106935408A CN106935408A CN201511024447.3A CN201511024447A CN106935408A CN 106935408 A CN106935408 A CN 106935408A CN 201511024447 A CN201511024447 A CN 201511024447A CN 106935408 A CN106935408 A CN 106935408A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010408 film Substances 0.000 claims abstract description 69
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010936 titanium Substances 0.000 claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 63
- 239000011521 glass Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 25
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000000873 masking effect Effects 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 57
- 239000000975 dye Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910010413 TiO 2 Inorganic materials 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000208340 Araliaceae Species 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007248 cellular mechanism Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000013083 solar photovoltaic technology Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to dye-sensitized solar cell anode and preparation method thereof, the preparation method includes：The previously prepared precursor solution including titanium source is attached on the conducting surface of transparent conducting glass, evaporation makes to form meso-hole structure titanium deoxid film layer；The transparent conducting glass low-temperature bake of the meso-hole structure titanium deoxid film layer will be formed with, the meso-hole structure titanium deoxid film layer of metastable condition is obtained；Repeat the transparent conducting glass that foregoing 2 steps obtain the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer；The transparent conducting glass of the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer is carried out into high-temperature roasting, the meso-hole structure titanium dioxide thin film photo-anode of stable state is obtained.
Description
Technical field
The invention belongs to field of dye-sensitized solar cells, more particularly to a kind of light anode of DSSC
Preparation method, the light anode of DSSC and the dye sensitization comprising the light anode be too as obtained in methods described
Positive energy battery.
Background technology
Revolutionary change is brought to the energy consumption structure of the mankind with the Solar use that solar-photovoltaic technology is support
Change.Compared with traditional silica-based solar cell, and dye-sensitized solar cells (Dye-Sensitized Solar Cell, referred to as
DSSC) have cheap cost, rich in natural resources, the performance of stabilization, production process simple, nontoxic, pollution-free and suitable big
The advantages such as large-scale production.DSSC has huge price advantage with respect to other solar cells simultaneously, according to estimating
Meter, the cost of DSSC is only 1/5~1/10, DSSC of silicon solar cell will be as a kind of competitive commercialization
Product.
Dye-sensitized solar cells are a kind of photoelectrochemical solar cells, and it is mainly by nano crystal semiconductor optical anode, dyestuff
Sensitizer, electrolyte and to the part of electrode four constitute.Wherein light anode is the core component of DSSC batteries, its structure and group
Into the photovoltaic performance for affecting battery strongly, particularly conversion efficiency.
DSSC (DSSC) was developed in 1991.They are to use lower cost materials system
Make, and the equipment that their manufacture need not be complicated.Two kinds of functions that they will be provided by silicon are separated：The main body of semiconductor is used
Produced by separate light-sensitive coloring agent in electric charge conveying and photoelectron.DSSC is the sandwich knot shown in Fig. 1
Structure, and prepared typically via following steps：There is provided by electrically conducting transparent stannic oxide film (FTO) glass plate of fluorine doped；
The slurry of the lateral coated glass plate metal oxides (usually titanium dioxide) of FTO；The plate is heated to about
450-500 DEG C of the temperature time of at least 1 hour；By above-mentioned coated board impregnated in dye solution time of about 24 hours with
The dyestuff is set to be covalently bond to the surface of titanium dioxide；Another platinum that is coated with is provided to electrode glass sheet；By this two pieces of glass plates
Seal and introduce electrolyte solution between the plates, the metal oxide and electrolyte bag of (dye) will be dyeed in two conductive plates
Between and prevent electrolyte leakage.
In such dye-sensitized cell, photon strikes dyestuff makes dye transfer to can inject electrons into titanium dioxide
Excitation state in titanium light anode conduction band, the electronics diffuses to anode from the conduction band of the titanium dioxide.From dyestuff/TiO2System
The electronics for losing is given back by the way that iodide are oxidized into teriodide to electrode, and the reaction is sufficiently fast so that photochemistry efficiency
Can continue to.
DSSC produce about 0.8V can be compared with the ceiling voltage of silicon solar cell ceiling voltage.DSSC is compared to silicon
One important advantage of solar cell is during dye molecule injects electrons into titanium dioxide conduction band, to produce excitation state dye molecule
Electron vacancy is produced rather than in neighbouring solid, so as to reduce the quick compound of electrons.Therefore, they can so do
Low optical condition under run：Under the low optical condition, electron/hole-recombination is changed into mastery in silicon solar cell
Mechanism.
The major defect of DSSC is long-time necessary to dyeing titania nanoparticles：Make for solar cell
12-24 hours is spent using the dyeing of necessary titanium dioxide layer.
Accordingly, it would be desirable to a kind of light anode preparation method of the efficient quick of DSSC, enables quick
The as far as possible many dyestuffs of absorption.
The content of the invention
For the disadvantages described above of prior art, it is an object of the invention to provide a kind of the efficient of DSSC
Efficiently light anode preparation method.
Here, the present invention provides a kind of dye-sensitized solar cell anode preparation method, the preparation method includes：
The previously prepared precursor solution including titanium source is attached on the conducting surface of transparent conducting glass, evaporation makes to form meso-hole structure
Titanium deoxid film layer；
The transparent conducting glass low-temperature bake of the meso-hole structure titanium deoxid film layer will be formed with, the mesoporous knot of metastable condition is obtained
Structure titanium deoxid film layer；
Repeat the meso-hole structure titanium dioxide that foregoing 2 steps obtain the metastable condition with multilayer (namely at least more than 2 layers)
The transparent conducting glass of film layer；
The transparent conducting glass of the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer is carried out into high-temperature roasting, is obtained steady
Determine the meso-hole structure titanium dioxide thin film photo-anode of state.
The present invention prepares individual layer titanium deoxid film using lifting film-forming method in the substrate of FTO glass；Evaporation makes dioxy
Change titanium film and form meso-hole structure；Heating makes meso-hole structure titanium deoxid film tend to metastable condition；It is situated between with making multilayer repeatedly
Pore structure titanium deoxid film；The meso-hole structure titanium dioxide thin film photo-anode of final high temperature sintering generation stable state.This method
The thickness being made is that 10 μm of light anode has up to 18.62*10-8mol/cm2Dye Adsorption rate, this be derived from meso-hole structure
Specific surface area (the 129m of titanium dioxide2g-1Left and right, Fig. 1 is test curve) it is about existing commercial dyes sensitization solar battery
Light anode material P25 specific surface areas (50m2g-1Left and right) 2.5 times, and the latter correspondence light anode Dye Adsorption rate exist
11.54*10-8mol/cm2Left and right, also with good photoelectric transformation efficiency, (preferred 5 Rotating fields photoelectric transformation efficiency is 3.8-
5.0%), while preparation method is again simple and easy to apply, beneficial to regulation and control parameters, it is particularly well-suited to DSSC
Make.
It is preferred that the titanium source is at least in isopropyl titanate, the positive fourth fat of metatitanic acid, titanium tetrachloride, titanium trichloride
Kind.
It is preferred that titanium elements mass percent is 1%~1.5% in the precursor solution.It is embedding that the pore creating material is preferably three
Section copolymer F127 and/or P123.
In the present invention, the preparation process of the precursor solution can be prepared as follows, including：By pore creating material and nothing
Water-ethanol is uniformly mixed to get solution A；The ratio of hydrochloric acid solution and water in mass ratio 2~2.5 is mixed to get solution B, its
In, the molar concentration of hydrochloric acid is 10mol/L~12mol/L in hydrochloric acid solution；It is according to mass ratio with solution B by solution A
4.5~5 are uniformly mixed to get solution C；Titanium source is slowly dropped into solution C and continues stirring, mixing time 1~2 hour.
The making of meso-hole structure titanium deoxid film layer of the present invention can be made using czochralski method.It is preferred that the czochralski method
The process conditions of masking are：Transparent conducting glass is immersed by precursor solution with the mm/min of decrease speed 200~400, is stood
50~300 seconds, transparent conducting glass is lifted out by precursor solution with the mm/min of the rate of climb 50~100.
It is preferred that the evaporation includes：The transparent conducting glass that precursor solution will be attached to is placed in saturation magnesium nitrate, satisfies
Evaporated 6~12 hours with the environment that the humidity of sodium bromide or saturated solution of potassium iodide construction is 50~70%.
It is preferred that the sintering temperature of the low-temperature bake is 80~150 DEG C, roasting time is 20~60 minutes.
It is preferred that the thickness of the meso-hole structure titanium deoxid film of the stable state is 0.45~0.55 micron.
It is preferred that the sintering temperature of high-temperature roasting is 300~400 DEG C, roasting time is 150~200 minutes, heating rate
0.8~1.2 DEG C/min.
The present invention also aims to provide a kind of light anode, the light anode is prepared by above-mentioned preparation method.
Another object of the present invention is also resided in and provides a kind of DSSC of high-photoelectric transformation efficiency, the dye
Material sensitization solar battery includes above-mentioned light anode, such as by electrically conducting transparent stannic oxide film (FTO) glass of fluorine doped, light sun
Pole, light-sensitive coloring agent, conductive electrolyte, the DSSC of platinum plating electro-conductive glass composition.
Brief description of the drawings
Fig. 1 is the structural representation of DSSC；
Fig. 2 is mesoporous TiO 2 hole adsorption curve；
Fig. 3 is mesoporous TiO 2 graph of pore diameter distribution；
Fig. 4 is mesoporous TiO 2 transmission electron microscope picture；
Fig. 5 is 1,3,5 layers of mesoporous titanium dioxide film light anode I-V curve figure (embodiment 1)；
Fig. 6 is the X-ray diffractogram of mesoporous titanium dioxide powder；
Fig. 7 is mesoporous titanium dioxide film light anode ESEM sectional view；
Fig. 8 is 1,3,5 layers of mesoporous titanium dioxide film light anode I-V curve figure (embodiment 2).
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following implementation methods, it should be appreciated that following implementation methods are only used for
The bright present invention, is not intended to limit the present invention.
The invention provides a kind of DSSC of the meso-hole structure titanium deoxid film layer made with multilayer
Light anode.It includes making the step of forming the precursor solution of meso-hole structure titanium deoxid film layer and in FTO
The step of meso-hole structure titanium deoxid film layer with multilayer is formed on glass.Wherein, for the formation on FTO glass
Meso-hole structure titanium deoxid film layer, often forming one layer and first carrying out low-temperature bake makes the meso-hole structure titanium deoxid film layer be
Metastable condition, multilayer is concatenated to form with this, then by the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer
Transparent conducting glass carries out high-temperature roasting, so that meso-hole structure titanium deoxid film layer is changed into stabilization shape by metastable condition
State, so as to the light anode of the meso-hole structure titanium deoxid film layer of the stable state having is obtained.
On precursor solution, wherein pore creating material can be added, and absolute alcohol is used as solvent.Pore creating material, anhydrous second
Alcohol, titanium elements can be according to mass ratioes 1：16~20：0.7~1.6 ratio is mixed.Titanium source can be metatitanic acid isopropyl
The positive fourth fat of ester, metatitanic acid, titanium tetrachloride, titanium trichloride etc..
When preparing precursor solution, can be prepared by the following method：Pore creating material and absolute ethyl alcohol are uniformly mixed to get
Solution A；Hydrochloric acid solution and water are mixed to get solution B；Solution A and solution B are uniformly mixed to get solution C；Stirring shape
Titanium source is slowly dropped into solution C under state and continues stirring, mixing time obtains precursor solution in 1~2 hour, wherein, pore-creating
Agent：Absolute ethyl alcohol：The ratio of titanium source is 1：16~20：0.7~1.6, the preferred triblock copolymer F127 of pore creating material,
P123, more preferably F127.The role of hydrochloric acid solution is adjustment solution acid alkalinity so that solution is slightly presented acidity, keeps away
Occur precipitation, the preferred 10mol/L~12mol/L of hydrochloric acid solution molar concentration after exempting from, solution A is according to mass ratio with solution B
4.5~5.
Can utilize the method for lifting masking that forerunner's liquor is attached on FTO glass, then evaporation makes its autonomous dress shape
The meso-hole structure titanium deoxid film layer is set to be formed as meta-stable shape into meso-hole structure titanium deoxid film layer, then low-temperature bake
State.The lifting, evaporation, low-temperature bake process are repeated multiple times, such that it is able to obtain the mesoporous knot of the metastable condition with multilayer
The transparent conducting glass of structure titanium deoxid film layer.
On lift masking process conditions can be：Transparent conducting glass is immersed with 200~400mm/min of decrease speed
Precursor solution, soaks 50-300s in precursor solution, is lifted out FTO with rate of climb 50-100mm/min above-mentioned
Precursor liquid.In the preparation method of film, the film prepared using the method for lifting masking has that thickness is uniform, film surface is put down
The advantages of whole, good process repeatability.
On evaporation process, independently dress forms meso-hole structure can to select the natural evaporation in the environment of constant humidity.As
One example, more specifically：The FTO glass comprising forerunner's liquid layer that above-mentioned treatment is completed is placed in saturation magnesium nitrate molten
The humidity that liquid, saturation sodium bromide or saturation KI are built for 50%~70% (such as 60%) room temperature environment in steam naturally
Hair 6-12h, makes precursor solution therein that the process of autonomous dress is completed in evaporation, and the titanium dioxide for forming meso-hole structure is thin
Film.In the environment of such humidity range, can cause that the meso-hole structure of titanium deoxid film is more preferably formed, and cause each
The effect of natural evaporation is consistent, it is to avoid the change of humidity environment brings the deviation of experimental result.
Roasting under cryogenic forms the meso-hole structure titanium deoxid film layer of metastable condition.As an example, more
In particular：The FTO sheet glass that autonomous dress will be completed and mesoporous TiO 2 structure is formed is placed in 80-150 DEG C of baking oven and puts
Put 20-60min.
After lifting, evaporation, low-temperature bake process are repeated multiple times, the meta-stable shape of multilayer can be formed in transparent conducting glass
The meso-hole structure titanium deoxid film layer of state.Wherein, the present invention " multiple " that refers to, refer to more than 2 times and including 2 times
It is interior；And " multilayer " that the present invention is referred to, refer to more than 2 layers and including including 2 layers.
The transparent conducting glass of the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer is carried out into high temperature roasting
Burn, then the meso-hole structure titanium dioxide thin film photo-anode of stable state can be obtained.High-temperature roasting operation mainly can be in high temperature ring
Cause that organic pore-forming agents react with air, generate escaping gas under border, so as to pure titanium deoxid film is obtained.
Used as an example, the operation of high-temperature roasting more specifically can be：Heating rate according to 1 DEG C/min is warmed up to
350 DEG C, kept for 350 DEG C continue 180min, Temperature fall forms the meso-hole structure titanium deoxid film light sun of rock-steady structure
Pole.
It is characteristic of the invention that：Preparation method of the invention can shorten make titania nanoparticles dye needed for when
Between, it is a kind of light anode preparation method of efficient quick, can quickly adsorb as far as possible many dyestuffs.The light that this method is made
Anode has Dye Adsorption rate higher, and the thickness that this method is made is that 10 μm of light anode has up to 18.62*10- 8mol/cm2Dye Adsorption rate, this be derived from meso-hole structure titanium dioxide specific surface area (129m2g-1Left and right, Fig. 1 is test
Curve) it is about existing commercial dyes sensitization solar battery light anode material P25 specific surface areas (50m2g-1Left and right) 2.5
Times, and the Dye Adsorption rate of the latter's correspondence light anode is 11.5410-8mol/cm2Left and right, also with good photoelectric transformation efficiency
(preferred 5 Rotating fields photoelectric transformation efficiency is 3.8-5.0%), while preparation method is again simple and easy to apply, beneficial to the every ginseng of regulation and control
Number, is particularly well-suited to the making of DSSC.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
Bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is of the invention
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by the explanation of this paper
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
(1) F127 [trade names are utilized：Pluronics is a kind of water miscible polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-
PEO) three-stage copolymer] used as pore creating material, isopropyl titanate prepares precursor solution needed for light anode, specific step as titanium source
Suddenly include：
A) absolute ethyl alcohol of 22g (27.5ml) is added in the pore creating material F127 of 1.26g, is stirred, labeled as solution A；
B) hydrochloric acid solution that the content of 3.36g is 37% is mixed with the aqueous solution of 1.5g, labeled as solution B；
C) by solution A, B mixing is stirred until homogeneous, labeled as solution C；
D) the isopropyl titanate solution dropper of 1.68g is slowly added to the solution C in stirring, continues to stir 2h until clarification, mark
It is solution D, solution D is precursor solution needed for preparation light anode needed for us；
E) solution D is dried into sample preparation, Fig. 2 is the hole adsorption curve for characterizing mesoporous TiO 2, represents respectively and titanium deoxid film is added
To the adsorbance of nitrogen molecule under different partial pressures during pressure and decompression, titanium deoxid film has space as seen from Figure 2
Structure, Fig. 3 is the graph of pore diameter distribution for characterizing mesoporous TiO 2, and the membrane pore size is distributed in 100nm as seen from Figure 3
Left and right, is meso-hole structure really, and Fig. 4 is the transmission electron microscope picture for characterizing mesoporous TiO 2 meso-hole structure, can be more by Fig. 4
Intuitively find out the meso-hole structure of titanium deoxid film, Fig. 6 is that the X-ray for characterizing mesoporous titanium dioxide powder lattice structure is spread out
Figure is penetrated, the titanium deoxid film is the structure of Anatase as seen from Figure 6.
(2) tin ash (SnO for lifting film-making machine in doping fluorine (F) is utilized2) transparent conducting glass (hereinafter referred to as FTO
Glass) on be obtained individual layer mesoporous TiO 2 (TiO2)：
A) choose the FTO that monolithic area is the ㎝ of 1.5 ㎝ * 2.5 a piece of, its conducting surface is measured using universal meter；
B) in the above-mentioned precursor liquid of lower half end intrusion with decrease speed 300mm/min by FTO, 60s is stood；
C) FTO is lifted out by above-mentioned precursor liquid with rate of climb 75mm/min, film needed for being obtained thereon；
D) the remaining precursor liquid of above-mentioned FTO nonconductive surfaces is washed with ethanol solution；
E) it is 60% the FTO glass comprising forerunner's liquid layer that above-mentioned treatment is completed to be placed in into the humidity that saturation magnesium nitrate solution built
Natural evaporation 8h in room temperature environment, makes precursor solution therein that the process of autonomous dress is completed in evaporation, forms mesoporous dioxy
Change titanium layer.
(3) low-temperature heat makes meso-hole structure TiO2Film tends to metastable condition：
A) the FTO sheet glass that will be completed autonomous dress and form mesoporous TiO 2 structure is placed in placement 30min shapes in 120 DEG C of baking oven
Into the meso-hole structure TiO of metastable condition2Film light anode；
B) repeat the above steps (2) and step (3) in a) work form the metastable light with multi-layer mesoporous titanium deoxid film structure
Anode.
Fig. 7 characterizes the thickness of the mesoporous titanium dioxide film light anode under ESEM, is sweeping as seen from Figure 7
We can clearly measure the thickness of titanium deoxid film in the Electronic Speculum sectional drawing of face.
(4) high-temperature heating forms the multi-layer mesoporous titanium dioxide thin film photo-anode of rock-steady structure：
A) 350 DEG C are warmed up to according to the heating rate of 1 DEG C/min；
B) 180min is kept at 350 DEG C；
C) Temperature fall is obtained final mesoporous titanium dioxide film light anode structure to room temperature.
The different mesoporous TiO of table 12The corresponding light anode thickness of the number of plies
| Mesoporous TiO2The number of plies | 1 | 3 | 5 |
| Light anode thickness | 0.52μm | 1.45μm | 2.56μm |
The FTO glass of prepared mesoporous titanium dioxide film light anode structure is placed into dyestuff and soaks 8h.
Other DSSC structures shown in additional figure 1 above, measure light anode as shown in Figure 5 and are respectively 1 layer, 3 layers respectively
The I-V curve of the DSSC of the mesoporous titanium dioxide film composition with 5 layers, and draw its photoelectric efficiency be respectively 2.02%,
3.11% and 4.82%；
Photoelectric transformation efficiency computing formula is used：
Efficiency (%)=FF × Jsc × Voc/p
Wherein FF is fill factor, curve factor (Fill Factor), and Jsc is short-circuit current density (Short circuit current density), Voc
It is open-circuit voltage (Open-circuit voltage), Pin is instantaneous luminous energy density (Incident light power density).
Embodiment 2
Precursor solution needed for light anode is prepared collectively as titanium source as pore creating material, titanium tetrachloride and isopropyl titanate by the use of P123,
Specific steps include：
A) the pore creating material P123 of 1g is added into 20g (25ml) absolute ethyl alcohol, stirs 30min, until uniform clarification, labeled as molten
Liquid A；
B) 0.6g (350 μ l) titanium tetrachloride is slowly added to liquid-transfering gun under stirring, continues to stir, until clarification；
C) 1.7g isopropyl titanates are slowly added to liquid-transfering gun under stirring, until clarification, is designated as solution B；Solution B is for I
Needed for preparation light anode needed for precursor solution.
(2) tin ash (SnO for lifting film-making machine in doping fluorine (F) is utilized2) transparent conducting glass is (hereinafter referred to as
FTO glass) on be obtained individual layer mesoporous TiO 2 (TiO2)：
A) choose the FTO that monolithic area is the ㎝ of 1.5 ㎝ * 2.5 a piece of, its conducting surface is measured using universal meter；
B) in the above-mentioned precursor liquid of lower half end intrusion with decrease speed 250mm/min by FTO, 100s is stood；
C) FTO is lifted out by above-mentioned precursor liquid with rate of climb 100mm/min, film needed for being obtained thereon；
D) the remaining precursor liquid of above-mentioned FTO nonconductive surfaces is washed with ethanol solution；
E) it is 60% the FTO glass comprising forerunner's liquid layer that above-mentioned treatment is completed to be placed in into the humidity that saturation magnesium nitrate solution built
Natural evaporation 8h in room temperature environment, makes precursor solution therein that the process of autonomous dress is completed in evaporation, forms mesoporous dioxy
Change titanium layer.
(3) low-temperature heat makes meso-hole structure TiO2Film tends to metastable condition：
A) the FTO sheet glass that will be completed autonomous dress and form mesoporous TiO 2 structure is placed in 80 DEG C of baking oven and places 50min and formed
The meso-hole structure TiO of metastable condition2Film light anode；
B) repeat the above steps (2) and step (3) in a) work form the metastable light with multi-layer mesoporous titanium deoxid film structure
Anode.
(4) high-temperature heating forms the multi-layer mesoporous titanium dioxide thin film photo-anode of rock-steady structure：
A) 330 DEG C are warmed up to according to the heating rate of 1 DEG C/min；
B) 180min is kept at 330 DEG C；
C) Temperature fall is obtained final mesoporous titanium dioxide film light anode structure to room temperature.
The thickness of the mesoporous titanium dioxide film light anode being characterized under ESEM, obtains the different mesoporous TiO of table 22The number of plies
Corresponding light anode thickness
| Mesoporous TiO2The number of plies | 1 | 3 | 5 |
| Light anode thickness | 0.51μm | 1.55μm | 2.49μm |
The FTO glass of prepared mesoporous titanium dioxide film light anode structure is placed into dyestuff and soaks 8h.
Other DSSC structures shown in additional figure 1 above, measure respectively light anode as shown in Figure 8 be respectively 1 layer, 3
The I-V curve of layer, the DSSC of 5 layers of mesoporous titanium dioxide film composition, and show that its photoelectric transformation efficiency is respectively
2.03%th, 3.05% and 4.80%.
Industrial applicability：The light anode that the method for the present invention is made has Dye Adsorption rate higher, good opto-electronic conversion
Efficiency, while preparation method is again simple and easy to apply, beneficial to regulation and control parameters, is particularly well-suited to the system of DSSC
Make.
Claims (10)
1. a kind of dye-sensitized solar cell anode preparation method, it is characterised in that the preparation method includes：
The previously prepared precursor solution including titanium source is attached on the conducting surface of transparent conducting glass, evaporation makes to form meso-hole structure titanium deoxid film layer；
The transparent conducting glass low-temperature bake of the meso-hole structure titanium deoxid film layer will be formed with, the meso-hole structure titanium deoxid film layer of metastable condition is obtained；
Repeat the transparent conducting glass that foregoing 2 steps obtain the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer；
The transparent conducting glass of the meso-hole structure titanium deoxid film layer of the metastable condition with multilayer is carried out into high-temperature roasting, the meso-hole structure titanium dioxide thin film photo-anode of stable state is obtained.
2. preparation method according to claim 1, it is characterised in that the titanium source is at least one in isopropyl titanate, the positive fourth fat of metatitanic acid, titanium tetrachloride, titanium trichloride.
3. preparation method according to claim 1 and 2, it is characterised in that titanium elements mass percent is 1%~1.5% in the precursor solution.
4. preparation method according to any one of claim 1 to 3, it is characterised in for preparing the meso-hole structure titanium deoxid film layer using lifting legal system, the process conditions of the czochralski method masking are：Transparent conducting glass is immersed by precursor solution with the mm/min of decrease speed 200~400,50~300 seconds are stood, transparent conducting glass is lifted out by precursor solution with the mm/min of the rate of climb 50~100.
5. preparation method according to any one of claim 1 to 4, it is characterised in that the evaporation includes：The transparent conducting glass of precursor solution will be attached to and be placed in evaporation 6~12 hours in the environment that the humidity of saturation magnesium nitrate solution, saturation sodium bromide or saturation KI construction is 50~70%.
6. preparation method according to any one of claim 1 to 5, it is characterised in that the sintering temperature of the low-temperature bake is 80~150 DEG C, roasting time is 20~60 minutes.
7. preparation method according to any one of claim 1 to 6, it is characterised in that the thickness of the meso-hole structure titanium deoxid film of the stable state is 0.45~0.55 micron.
8. preparation method according to any one of claim 1 to 7, it is characterised in that the sintering temperature of high-temperature roasting is 300~400 DEG C, roasting time is 150~200 minutes, 0.8~1.2 DEG C/min of heating rate.
9. a kind of light anode, it is characterised in that the light anode is prepared as the preparation method any one of claim 1 to 8.
10. a kind of DSSC, it is characterised in that including the light anode described in claim 9.
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| CN101385968A (en) * | 2008-10-30 | 2009-03-18 | 上海交通大学 | Preparation method of photochemical catalyst activated carbon doped titanium dioxide nano material |
| CN102176383A (en) * | 2011-03-16 | 2011-09-07 | 上海交通大学 | Method for preparing multilayer titanium dioxide mesoporous film electrode for solar batteries |
| CN102173450A (en) * | 2009-06-03 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Preparation method of titanium dioxide film |
| CN103383897A (en) * | 2012-05-02 | 2013-11-06 | 中国人民解放军国防科学技术大学 | Method for preparing photo-anode of dye-sensitized solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385968A (en) * | 2008-10-30 | 2009-03-18 | 上海交通大学 | Preparation method of photochemical catalyst activated carbon doped titanium dioxide nano material |
| CN102173450A (en) * | 2009-06-03 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Preparation method of titanium dioxide film |
| CN102176383A (en) * | 2011-03-16 | 2011-09-07 | 上海交通大学 | Method for preparing multilayer titanium dioxide mesoporous film electrode for solar batteries |
| CN103383897A (en) * | 2012-05-02 | 2013-11-06 | 中国人民解放军国防科学技术大学 | Method for preparing photo-anode of dye-sensitized solar cell |
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