CN103366961A - Doped titanium dioxide and preparation method thereof as well as dye-sensitized solar cell - Google Patents
Doped titanium dioxide and preparation method thereof as well as dye-sensitized solar cell Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 340
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 18
- 230000004044 response Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003608 titanium Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002042 Silver nanowire Substances 0.000 abstract 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 32
- 239000000843 powder Substances 0.000 description 20
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 16
- 229960004889 salicylic acid Drugs 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 12
- 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 description 12
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 10
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
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- 238000012546 transfer Methods 0.000 description 8
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- 239000001856 Ethyl cellulose Substances 0.000 description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 6
- 229920001249 ethyl cellulose Polymers 0.000 description 6
- 235000019325 ethyl cellulose Nutrition 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 6
- 239000006256 anode slurry Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
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- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- -1 wherein Chemical compound 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- LWMDPZVQAMQFOC-UHFFFAOYSA-N 4-butylpyridine Chemical compound CCCCC1=CC=NC=C1 LWMDPZVQAMQFOC-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical group CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
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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
Abstract
The invention discloses a doped titanium dioxide and a preparation method thereof as well as a dye-sensitized solar cell, wherein the doped titanium dioxide is structurally characterized in that a crystalline titanium dioxide is doped with a silver nanowire. Sine the silver nanowire is of a linear structure and is very fine, the silver nanowire is higher in connectivity; and the linear silver nanowire enables adjacent titanium dioxide particles to be connected better, so that the three-dimensional net structure of the doped titanium dioxide is better in connectivity, and the transmittability of electrons is enhanced in the three-dimensional net structure. As the transmittability of the silver nanowire on the electrons is very strong, the electron energy loss of the doped titanium dioxide is avoided at the crystal interface of the titanium dioxide during electron conduction, and the electron conduction capacity of the doped titanium dioxide is very strong. The doped titanium dioxide enables the electrons to be quickly conducted to a conductive substrate of a photo-anode of the dye-sensitized solar cell made from the doped titanium dioxide, and the electro-optical transmission efficiency of the cell is increased.
Description
Technical field
The invention belongs to the DSSC technical field, be specifically related to titanium dioxide of a kind of doping and preparation method thereof, DSSC.
Background technology
Solar cell can directly be converted to electric energy with solar energy, mainly comprises: silicon is battery, compound semiconductor battery, polymer solar cells, DSSC.At present, the silicon solar cell occuping market principal status of public economy, but because the discharging of toxic byproduct being arranged in its cost costliness and the manufacture process in a large number, greatly limited the application of silicon solar cell, and low cost and environmentally friendly dye-sensitized solar cells will become the third generation solar cell that substituted for silicon is solar cell.Professor Greatzel of the engineering institute leaders' such as Lausanne, SUI height in 1991 research group is the TiO of nanoporous
2Be applied to DSSC (DSSC) and obtained breakthrough.Because the potential application prospect of DSSC, numerous commercial companies and research institution drop into a large amount of strength to the research of large-area DSSC.
DSSC consists of the following components: light anode, photocathode, electrolyte, dyestuff, be that the light anode that main body consists of is the skeleton part of battery by nano thin-film wherein, being not only support and the absorption carrier of dyestuff, also is the transport vehicle of electronics simultaneously.The parameters such as the voidage of nano thin-film, aperture, thickness, crystal formation, the adsorbance, electronics that directly affects dyestuff in the DSSC from dyestuff excitation state to electro-conductive glass transmission and electrolyte oxidation-right effective transmission of reduction electricity.Therefore, the light anode is the emphasis of research and development extensive concern as the important component part of DSSC always.
The at present research for dye-sensitized solar cell anode focuses mostly at the preferred and preparation technology's who attempts novel semiconductor material, light anode slurry additive the aspects such as optimization, purpose is to improve semi-conducting material to the utilance of sunlight and reduce injects semiconductor electronics and electrolytical compound, but for the raising of the photoelectric efficiency of DSSC ideal very.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in the prior art, titanium dioxide of a kind of doping and preparation method thereof, DSSC are provided, the nano silver wire connectedness with linear structure in the titanium dioxide of this doping is good, strong to the conducting power of electronics, has greatly improved the electronic conduction ability of the titanium dioxide that mixes.
Solve the titanium dioxide that technical scheme that the technology of the present invention problem adopts provides a kind of doping, its structure is to be doped with nano silver wire in the titanium dioxide of crystalline state.
Preferably, the mol ratio of the titanium dioxide of described crystalline state and described nano silver wire is (49: 1)～(29: 1).
Preferably, the diameter of described nano silver wire is that 10～50nm, length are 100～800nm.
Preferably, the particle diameter of described titanium dioxide is 20～50nm.
The invention provides a kind of preparation method who prepares the titanium dioxide of above-mentioned doping, may further comprise the steps:
(1) uses the amorphous titanium dioxide of Liquid preparation methods, obtain the suspension of described amorphous titanium dioxide, add again nano silver wire, obtain the first mixture;
(2) described the first mixture is put in the hydrothermal reaction kettle, added the titanium dioxide that thermal response obtains mixing, comprise titanium dioxide and the described nano silver wire of crystalline state in the titanium dioxide of this doping.
Preferably, the method for the amorphous titanium dioxide of described use Liquid preparation methods in the described step (1) is specially: the first acid inhibitor is joined in the first titanium salt aqueous solution, mix afterreaction and obtain described amorphous titanium dioxide.
Preferably, described the first titanium salt in the described step (1) is one or several mixtures in butyl titanate, isopropyl titanate, the ammonium titanium fluoride; Described the first acid inhibitor is salicylic acid and/or polyacrylic acid.
Preferably, the hydrionic mol ratio in the titanium ion in the first titanium salt aqueous solution described in the described step (1) and described the first acid inhibitor is (1: 10)～(2: 1).
Preferably, the concentration of the described titanium salt aqueous solution is 0.05～0.5M.
Preferably, the concentration of described acid inhibitor is 0.1～2M.
Preferably, the temperature of the described heating in the described step (2) is 140～170 ℃, and the time of described heating is 10～20 hours.
The invention provides a kind of preparation method who prepares the titanium dioxide of above-mentioned doping, may further comprise the steps:
(1) use the amorphous titanium dioxide of Liquid preparation methods, obtain the suspension of described amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture;
(2) described the second mixture is put into hydrothermal reaction kettle, add the titanium dioxide that thermal response obtains crystalline state, the titanium dioxide of this crystalline state is mixed the titanium dioxide that obtains mixing with nano silver wire.
Preferably, the method for the amorphous titanium dioxide of described use Liquid preparation methods in the described step (1) is specially: the second acid inhibitor is joined in the second titanium salt aqueous solution, mix afterreaction and obtain described amorphous titanium dioxide.
Preferably, described the second titanium salt in the described step (1) is one or several mixtures in butyl titanate, isopropyl titanate, the ammonium titanium fluoride; Described the second acid inhibitor is salicylic acid and/or polyacrylic acid.
Preferably, the hydrionic mol ratio in the titanium ion in the second titanium salt aqueous solution described in the described step (1) and described the second acid inhibitor is (1: 10)～(2: 1).
Preferably, the concentration of the described titanium salt aqueous solution is 0.05～0.5M.
Preferably, the concentration of described acid inhibitor is 0.1～2M.
Preferably, the temperature of the described heating in the described step (2) is 140～170 ℃, and the time of described heating is 10～20 hours.
The present invention also provides a kind of DSSC, the light anode of the DSSC that its titanium dioxide that contains above-mentioned doping is made.
Mixed nano silver wire in the titanium dioxide of the doping among the present invention, because nano silver wire is linear structure and very thin, so its connectivity is stronger, the nano silver wire that this is linear is so that better couple together between the contiguous titanium dioxide granule, thereby so that the connectedness of the three-dimensional net structure of the titanium dioxide of this doping improves, strengthened the transmittability of electronics in this three-dimensional net structure.Because nano silver wire is very strong to the conducting power of electronics, at the electron energy loss at the grain boundary place of titanium dioxide, the electronic conduction ability of the titanium dioxide of doping was very strong when the titanium dioxide of this doping had been avoided electrical conductivity.The titanium dioxide that mixes has improved the photoelectricity transmission efficient of battery so that electronics can be transmitted on the conductive substrates of light anode of the DSSC of being made by the titanium dioxide of this doping very soon.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that uses the titanium deoxid film of the doping on the light anode of the DSSC that the titanium dioxide of the doping of the embodiment of the invention 1 preparation makes;
Fig. 2 is the I-V detection figure of DSSC corresponding to the light anode that uses the titanium dioxide of the doping of the embodiment of the invention 1 preparation to make.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) polyacrylic acid with 2M slowly joins in the butyl titanate aqueous solution of 0.4M, wherein, hydrionic mol ratio in titanium ion in the butyl titanate aqueous solution and the polyacrylic acid of adding is 1: 10, at room temperature continue to stir 1 hour, reaction generates the suspension of amorphous titanium dioxide, again to wherein adding nano silver wire, wherein, the diameter of nano silver wire is that 10～30nm, length are 100～400nm, obtains the first mixture.
(2) all transfer to above-mentioned the first mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 60%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 170 ℃, the time of heating is 10 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 15 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, the titanium dioxide of this white powder for mixing, the titanium dioxide and the nano silver wire that comprise crystalline state in the titanium dioxide of this doping, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 49: 1.Owing to containing nano silver wire and amorphous titanium dioxide in the first mixture, the first mixture is as the predecessor of hydro-thermal reaction, so in the process of hydro-thermal reaction, carrying out along with hydro-thermal reaction, the titanium dioxide of crystalline state can deposit on the nano silver wire, and the titanium dioxide that is accompanied by the deposition process crystalline state is grown up gradually, between the titanium dioxide of crystalline state and nano silver wire, form so certain adhesion, and this adhesion is stronger, is conducive to strengthen the titanium dioxide of crystalline state and the photoelectricity transmission between the nano silver wire.
The titanium dioxide of the doping that the present embodiment is made is done the ultrasonic dispersion of dispersant with ethanol, again to wherein adding terpinol and ethyl cellulose, wherein, the mass ratio of ethyl cellulose and terpinol is 1: 6, the ethyl cellulose that adds and the gross mass umber of terpinol and the ratio of quality and the number of copies of nano titanium oxide are 3: 1, the light anode slurry that stirs and obtain used by dye sensitization solar battery.
Above-mentioned light anode slurry stirred after one hour, this slurry is filmed at electro-conductive glass, with the 450 ℃ of calcinings 30 minutes in Muffle furnace of the electro-conductive glass that coats film, cool to room temperature, form the titanium deoxid film that mixes at electro-conductive glass, thickness on the electro-conductive glass obtains the light anode of DSSC between 8～15 μ m.It is 5 * 10 that this light anode is soaked in concentration
-4The ruthenium complex N719 dyestuff [English name: RuL of mol/L
2(NCS)
22TBA(L=2,2 '-bipyridyl-4,4 '-dicarboxylic acid)] 24h in the ethanolic solution, the light anode is by the abundant sensitization of dyestuff.Then this light anode is docked electrode with platinum, splash into electrolyte, be assembled into DSSC, electrolyte comprises the LiI of 1M, the I of 0.1M
2, 0.5M the 4-butyl-pyridinium, wherein solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).
Titanium deoxid film on the light anode of the DSSC that said method is made is taken the photo of ESEM, as shown in Figure 1, the diameter of nano silver wire is that 10～30nm, length are 100～400nm, the particle size range of the titanium dioxide of crystalline state is 20～30nm, the particle size range that can be found out the titanium dioxide of the diameter of nano silver wire and crystalline state by the photo of this ESEM approaches, so that nano silver wire fully contacts with the titanium dioxide of crystalline state, thereby realize photoelectronic effective transmission between the titanium dioxide of nano silver wire and crystalline state.Simultaneously, nano silver wire also has dimensional effect and quantum effect, can cause the surface plasma resonance effect by solar light irradiation, strengthen the absorption to the luminous energy of sunlight, can improve the photoelectric efficiency of the DSSC of being made by the titanium dioxide of this doping.The titanium dioxide of crystalline state is particulate material, and electronics has certain electron energy loss when the titanium dioxide conduction of granular crystalline state.Nano silver wire is linear structure, and its electronic conduction ability is better than the titanium dioxide of granular crystalline state greatly, owing in the titanium dioxide of the doping that makes in the present embodiment nano silver wire is arranged, so the electronic conduction ability of the titanium dioxide of this doping strengthens greatly.
DSSC in the present embodiment comprises the light anode that uses above-mentioned nano titania slurry preparation.Use the xenon lamp simulated solar irradiation when this battery is surveyed efficient, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode), as shown in Figure 2, recording the cell photoelectric conversion efficiency that this membrane electrode forms under this light intensity is 6.81%, the short-circuit current density of battery is 15.0mA/cm
2, open circuit voltage is 0.703V, and fill factor, curve factor is 64.50%, and the photoelectric properties of this battery improve greatly.
Mixed nano silver wire in the titanium dioxide of the doping in the present embodiment, because nano silver wire is linear structure and very thin, so its connectivity is stronger, the nano silver wire that this is linear is so that better couple together between the contiguous titanium dioxide granule, thereby so that the connectedness of the three-dimensional net structure of the titanium dioxide of this doping improves, strengthened the transmittability of electronics in this three-dimensional net structure.Because nano silver wire is very strong to the conducting power of electronics, at the electron energy loss at the grain boundary place of titanium dioxide, the electronic conduction ability of the titanium dioxide of doping was very strong when the titanium dioxide of this doping had been avoided electrical conductivity.The titanium dioxide that mixes has improved the photoelectricity transmission efficient of battery so that electronics can be transmitted on the conductive substrates of light anode of the DSSC of being made by the titanium dioxide of this doping very soon.
Embodiment 2
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) salicylic acid with 0.1M slowly joins in the isopropyl titanate aqueous solution of 0.05M, wherein, hydrionic mol ratio in titanium ion in the isopropyl titanate aqueous solution and the salicylic acid of adding is 1: 1, at room temperature continue to stir 2 hours, reaction generates the suspension of amorphous titanium dioxide, again to wherein adding nano silver wire, wherein, the diameter of nano silver wire is that 20～40nm, length are 300～500nm, obtains the first mixture.
(2) all transfer to above-mentioned the first mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 70%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 140 ℃, the time of heating is 12 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 45 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains be positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, this white powder is the titanium dioxide of doping, comprises titanium dioxide and the nano silver wire of crystalline state in the titanium dioxide of this doping, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 32: 1, and the particle diameter of the titanium dioxide of crystalline state is 30～40nm.
Embodiment 3
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) with the salicylic acid of 1M and polyacrylic mixed solution (wherein, salicylic acid and polyacrylic mass ratio are 1: 1), slowly join in the ammonium titanium fluoride aqueous solution of 0.5M, wherein, hydrionic mol ratio in titanium ion in the ammonium titanium fluoride aqueous solution and the salicylic acid of adding and the polyacrylic mixed solution is 2: 1, at room temperature continue to stir 3 hours, reaction generates the suspension of amorphous titanium dioxide, again to wherein adding nano silver wire, wherein, the diameter of nano silver wire is that 10～30nm, length are 200～600nm, obtains the first mixture.
(2) all transfer to above-mentioned the first mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 80%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 150 ℃, the time of heating is 16 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 25 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, the titanium dioxide of this white powder for mixing, the titanium dioxide and the nano silver wire that comprise crystalline state in the titanium dioxide of this doping, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 26: 1.
Embodiment 4
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) salicylic acid of 1.5M is slowly joined in the mixed aqueous solution of the butyl titanate of 0.3M and isopropyl titanate (wherein, the mass ratio of butyl titanate and isopropyl titanate is 2: 1), wherein, hydrionic mol ratio in titanium ion in the mixed aqueous solution of butyl titanate and isopropyl titanate and the salicylic acid of adding is 1.5: 1, at room temperature continue to stir 2.5 hours, reaction generates the suspension of amorphous titanium dioxide, again to wherein adding nano silver wire, wherein, the diameter of nano silver wire is 30～50nm, length is 300～700nm, obtains the first mixture.
(2) all transfer to above-mentioned the first mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 75%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 160 ℃, the time of heating is 20 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 30 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains be positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, this white powder is the titanium dioxide of doping, comprises titanium dioxide and the nano silver wire of crystalline state in the titanium dioxide of this doping, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 29: 1, and the particle diameter of the titanium dioxide of crystalline state is 40～50nm.
Embodiment 5
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) polyacrylic acid with 0.1M slowly joins in the isopropyl titanate aqueous solution of 0.05M, wherein, hydrionic mol ratio in titanium ion in the isopropyl titanate aqueous solution and the polyacrylic acid of adding is 2: 1, at room temperature continue to stir 1.5 hours, generate amorphous titanium dioxide, obtain the suspension of amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture.
(2) all transfer to above-mentioned the second mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 75%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 140 ℃, the time of heating is 16 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 45 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, this white powder is the titanium dioxide of crystalline state, this white powder is mixed with nano silver wire, and wherein, the diameter of nano silver wire is 20～40nm, length is 400～800nm, the titanium dioxide that obtains mixing, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 29: 1, and the particle diameter of the titanium dioxide of crystalline state is 30～40nm.
The titanium dioxide of the doping that the present embodiment is made is done the ultrasonic dispersion of dispersant with ethanol, again to wherein adding terpinol and ethyl cellulose, wherein, the mass ratio of ethyl cellulose and terpinol is 1: 6, the ethyl cellulose that adds and the gross mass umber of terpinol and the ratio of quality and the number of copies of nano titanium oxide are 3: 1, the light anode slurry that stirs and obtain used by dye sensitization solar battery.
Above-mentioned light anode slurry stirred after one hour, this slurry is filmed at electro-conductive glass, with the 450 ℃ of calcinings 30 minutes in Muffle furnace of the electro-conductive glass that coats film, cool to room temperature, form the titanium deoxid film that mixes at electro-conductive glass, thickness on the electro-conductive glass obtains the light anode of DSSC between 8～15 μ m.In above-mentioned sintering process, form certain adhesion between the titanium dioxide of nano silver wire and crystalline state.
According to the method for preparing DSSC among the embodiment 1, the light anode that uses the present embodiment to make is made DSSC.Use the xenon lamp simulated solar irradiation when this battery is surveyed efficient, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode), recording the cell photoelectric conversion efficiency that this membrane electrode forms under this light intensity is 4.92%, the short-circuit current density of battery is 10.4mA/cm
2, open circuit voltage is 0.759V, fill factor, curve factor is 62.32%.
Embodiment 6
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) with the salicylic acid of 2M and polyacrylic mixed solution (wherein, salicylic acid and polyacrylic mass ratio are 1: 2) slowly join in the butyl titanate aqueous solution of 0.3M, wherein, hydrionic mol ratio in titanium ion in the butyl titanate aqueous solution and the salicylic acid of adding and the polyacrylic mixed solution is 1: 10, at room temperature continue to stir 2 hours, generate amorphous titanium dioxide, obtain the suspension of amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture.
(2) all transfer to above-mentioned the second mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 80%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 150 ℃, the time of heating is 20 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 15 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtain white powder, this white powder is the titanium dioxide of crystalline state, this white powder is mixed with nano silver wire, and wherein, the diameter of nano silver wire is 10～30nm, length is 100～400nm, the titanium dioxide that obtains mixing, wherein, the titanium dioxide of crystalline state and the mol ratio of nano silver wire are 35: 1, and the particle diameter of the titanium dioxide of crystalline state is 20～30nm.
Embodiment 7
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) salicylic acid with 0.8M slowly joins in the ammonium titanium fluoride aqueous solution of 0.1M, wherein, hydrionic mol ratio in titanium ion in the ammonium titanium fluoride aqueous solution and the salicylic acid of adding is 1: 2, at room temperature continue to stir 1 hour, generate amorphous titanium dioxide, obtain the suspension of amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture.
(2) all transfer to above-mentioned the second mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 60%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 170 ℃, the time of heating is 12 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 20 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtains white powder, this white powder is the titanium dioxide of crystalline state, this white powder is mixed with nano silver wire, wherein, the diameter of nano silver wire is 30～50nm, length is 400～800nm, the titanium dioxide that obtains mixing, wherein, the mol ratio of the titanium dioxide of crystalline state and nano silver wire is 40: 1.
Embodiment 8
The present embodiment provides a kind of preparation method of titanium dioxide of doping, may further comprise the steps:
(1) salicylic acid of 1.2M is slowly joined in the mixed aqueous solution of the butyl titanate of 0.5M and isopropyl titanate (wherein, the mass ratio of butyl titanate and isopropyl titanate is 1: 2), wherein, hydrionic mol ratio in titanium ion in the mixed aqueous solution of butyl titanate and isopropyl titanate and the salicylic acid of adding is 1: 1, at room temperature continue to stir 1 hour, generate amorphous titanium dioxide, obtain the suspension of amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture.
(2) all transfer to above-mentioned the second mixture in the hydrothermal reaction kettle, the compactedness of fixing this hydrothermal reaction kettle is 70%, with this reactor fit sealing, this hydrothermal reaction kettle is heated, the temperature of the heating of control hydro-thermal reaction is 160 ℃, the time of heating is 10 hours, obtain the titanium dioxide of crystalline state by adding thermal response, heat under these conditions after 30 minutes and naturally cool to room temperature, be washed to neutrality after pouring out supernatant liquor, with absolute ethanol washing 2 times, the solid that obtains is positioned in 90 ℃ the baking oven dry 1 hour, obtains white powder, this white powder is the titanium dioxide of crystalline state, this white powder is mixed with nano silver wire, wherein, the diameter of nano silver wire is 20～40nm, length is 300～600nm, the titanium dioxide that obtains mixing, wherein, the mol ratio of the titanium dioxide of crystalline state and nano silver wire is 49: 1.
Embodiment 9
The present embodiment provides a kind of light anode of DSSC, and its titanium dioxide by above-mentioned doping is made.
Embodiment 10
The present embodiment provides a kind of DSSC, and it contains the light anode of above-mentioned DSSC.
Be understandable that, above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (11)
1. the titanium dioxide of a doping is characterized in that, its structure is to be doped with nano silver wire in the titanium dioxide of crystalline state.
2. the titanium dioxide of doping according to claim 1 is characterized in that, the titanium dioxide of described crystalline state and the mol ratio of described nano silver wire are (49: 1)～(29: 1).
3. the titanium dioxide of doping according to claim 1 and 2 is characterized in that, the diameter of described nano silver wire is that 10～50nm, length are 100～800nm.
4. the titanium dioxide of doping according to claim 1 and 2 is characterized in that, the particle diameter of described titanium dioxide is 20～50nm.
5. a preparation method who prepares the titanium dioxide of doping claimed in claim 1 is characterized in that, may further comprise the steps:
(1) uses the amorphous titanium dioxide of Liquid preparation methods, obtain the suspension of described amorphous titanium dioxide, add again nano silver wire, obtain the first mixture;
(2) described the first mixture is put in the hydrothermal reaction kettle, added the titanium dioxide that thermal response obtains mixing, comprise titanium dioxide and the described nano silver wire of crystalline state in the titanium dioxide of this doping.
6. the preparation method of the titanium dioxide of doping according to claim 5, it is characterized in that, the method of the amorphous titanium dioxide of described use Liquid preparation methods in the described step (1) is specially: the first acid inhibitor is joined in the first titanium salt aqueous solution, mix afterreaction and obtain described amorphous titanium dioxide.
7. the preparation method of the titanium dioxide of doping according to claim 5 is characterized in that, the temperature of the described heating in the described step (2) is 140～170 ℃, and the time of described heating is 10～20 hours.
8. a preparation method who prepares the titanium dioxide of doping claimed in claim 1 is characterized in that, may further comprise the steps:
(1) use the amorphous titanium dioxide of Liquid preparation methods, obtain the suspension of described amorphous titanium dioxide, the suspension of this amorphous titanium dioxide is the second mixture;
(2) described the second mixture is put into hydrothermal reaction kettle, add the titanium dioxide that thermal response obtains crystalline state, the titanium dioxide of this crystalline state is mixed the titanium dioxide that obtains mixing with nano silver wire.
9. the preparation method of the titanium dioxide of doping according to claim 8, it is characterized in that, the method of the amorphous titanium dioxide of described use Liquid preparation methods in the described step (1) is specially: the second acid inhibitor is joined in the second titanium salt aqueous solution, mix afterreaction and obtain described amorphous titanium dioxide.
10. the preparation method of the titanium dioxide of doping according to claim 8 is characterized in that, the temperature of the described heating in the described step (2) is 140～170 ℃, and the time of described heating is 10～20 hours.
11. a DSSC is characterized in that, the light anode of the DSSC that its titanium dioxide that contains the described doping of claim 1～4 any one is made.
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| CN108766628A (en) * | 2018-05-16 | 2018-11-06 | 浙江大学 | The preparation method of nano silver wire-oxide sol composite transparent electrode |
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