CN102446632A - Optical anode slurry for dye-sensitized solar cell and preparation method thereof as well as optical anode for dye-sensitized solar cell and dye-sensitized solar cell - Google Patents
Optical anode slurry for dye-sensitized solar cell and preparation method thereof as well as optical anode for dye-sensitized solar cell and dye-sensitized solar cell Download PDFInfo
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- 239000006256 anode slurry Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 230000003287 optical effect Effects 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 281
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 109
- 239000000843 powder Substances 0.000 claims abstract description 104
- 239000002245 particle Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 37
- 206010070834 Sensitisation Diseases 0.000 claims description 33
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- 230000007062 hydrolysis Effects 0.000 claims description 7
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- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- 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 6
- 239000008187 granular material Substances 0.000 claims description 5
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 4
- SZQONNWOQFYRTL-UHFFFAOYSA-M CC(C([O-])=O)O.N.[Ti+4] Chemical compound CC(C([O-])=O)O.N.[Ti+4] SZQONNWOQFYRTL-UHFFFAOYSA-M 0.000 claims description 4
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 229910052724 xenon Inorganic materials 0.000 description 18
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- 238000012360 testing method Methods 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 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 9
- 239000012327 Ruthenium complex Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000007767 bonding agent Substances 0.000 description 9
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- 238000001354 calcination Methods 0.000 description 9
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
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- 229910052710 silicon Inorganic materials 0.000 description 9
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- 230000005693 optoelectronics Effects 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
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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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- 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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Abstract
The invention discloses optical anode slurry for a dye-sensitized solar cell and a preparation method thereof as well as an optical anode of the dye-sensitized solar cell prepared by utilizing the slurry and the dye-sensitized solar cell, wherein titanium dioxide in the slurry for the dye-sensitized solar cell is the mixture of two kinds of nanoscale titanium dioxides with different particle sizes, the mixture is formed by mixing prepared nano titanium dioxide powder with the particle size of 8-16nm and the specific surface area of 90-100m<2>/g, and P25 titanium dioxide powder proportionally, the optical anode prepared from the slurry fully makes use of the respective advantages of the large particles and the small particles, which ensures that the optical anode has higher optical capture efficiency, but also the photosensitized dye absorption amount is improved, the generation rate and conveying capability of photon-generated carriers are intensified, and the recombination process of the photon-generated carriers is reduced, thus the photoelectric conversion efficiency of the dye-sensitized solar cell is improved. The optical anode slurry, the preparation method thereof as well as the optical anode and the dye-sensitized solar cell provided by the invention are suitable for the high-efficiency preparation of the dye-sensitized solar cell.
Description
Technical field
The invention belongs to technical field of solar cell manufacturing, be specifically related to a kind of used by dye sensitization solar battery light anode slurry and preparation method thereof, dye-sensitized solar cell anode and DSSC.
Background technology
In global energy resource structure, disposable fossil energies such as oil, natural gas, coal occupy the principal status of public economy.Along with serious day by day with environmental pollution of falling sharply of fossil energy, the reproducible energy of exploitation cleaning is extremely urgent.In the foreseeable Future Time of the mankind, solar energy does not produce any environmental pollution as the inexhaustible clear energy sources of the mankind, receives the restriction of any geographical environment hardly.Since the nineties; Research group with headed by the M.Gratzel of engineering institutes such as Lausanne, SUI height has developed DSSC, and in solar cell market, DSSC has represented a new developing direction of solar cell; Have cost low, be easy to make; The relative conversion ratio advantages of higher of light current, though its stability and transformation efficiency were still waiting to improve in present stage, this battery still is considered to have most one type of solar cell of application prospect.DSSC is a kind of solar cell based on the development of plant chlorophyll photosynthesis principle, is a kind of solar cell that uses semiconductor material with wide forbidden band.Wide band gap semiconducter itself has higher thermodynamic stability and photochemical stability; Yet the non-constant of the ability of catching sunlight; But suitable dyestuff is adsorbed onto on the semiconductor surface,, can semi-conductive spectral response be widened visible region by means of the strong absorption of dyestuff to visible light; This phenomenon becomes semi-conductive sensibilization, and this semiconductor that is loaded with dyestuff is called the dye-sensitized semiconductor electrode.As the carrier of dyestuff absorption, nano titanium oxide since characteristics such as its photostability, nontoxic, high-specific surface area be widely used on the dye cell.
DSSC mainly comprises light anode, photocathode, four parts of dye well electrolyte.At present, photocathode, dye well electrolyte preparation method are compared all comparative maturity, and the height of dye-sensitized cell transformation efficiency depends on the preparation of light anode slurry to a great extent.The slurry of the light anode of DSSC includes the nano titanium oxide of absorbing dye photosensitizer, and nano titanium oxide is not only the support and the absorption carrier of opto-electronic conversion active material-dyestuff, also is the transmission body of electronics simultaneously.Each parameter of nano titanium oxide and performance directly influence the adsorbance of the dyestuff in the DSSC; And influence transmission and OR electrolyte the electricity right effective transmission of electronics from dyestuff excitation state to electro-conductive glass; Influence electric transmission speed, and then influence the optoelectronic transformation efficiency of dye-sensitized cell.
The preparation of the light anode slurry of DSSC at present; What adopt mostly is the pure slurry of certain particle diameter; Or micron order bulky grain and the short grained mode that combines of nanometer; Micron-sized bulky grain can form effective conductive network, and nano level granule can improve the adsorbance of dyestuff with big surface area.But the mixed slurry of this nanoscale and micron-sized titanium dioxide is reunited easily, and the DSSC optoelectronic transformation efficiency that the pure slurry of certain particle diameter or the mixed slurry of nanoscale and micron-sized titanium dioxide are made is low.Present nano titanium oxide particle diameter is many, and P25 is exactly one of them below 100nm, and P25 is can be through the nanoscale crystal titanium dioxide of business procurement acquisition, and particle diameter is about 25nm.In DSSC, the titanium dioxide particle diameter is too big, and the adsorption rate of dyestuff is low, is unfavorable for opto-electronic conversion; Particle diameter is too little, and the interface is too many, and interface potential barrier hinders electric transmission; Also be unfavorable for opto-electronic conversion, and particle diameter is too little, cost of material is high; Therefore should seek appropriate particle size,, increase photoelectric conversion rate to reduce cost.
Summary of the invention
Technical problem to be solved by this invention is nanocrystalline or the P25 titanium dioxide powder is nanocrystalline and mixture micron-sized titanium dioxide crystal prepares the not high deficiency of DSSC optoelectronic transformation efficiency of slurry to using the P25 titanium dioxide powder in the prior art; A kind of used by dye sensitization solar battery light anode slurry and preparation method thereof, used by dye sensitization solar battery light anode and DSSC are provided; This used as dye-sensitized solar cell photo-anode slurry is used for the making of DSSC, thereby improves the optoelectronic transformation efficiency of DSSC.
Solving the technical scheme that technical problem of the present invention adopted is a kind of light anode slurry of used by dye sensitization solar battery; Include ethyl cellulose, terpinol and titanium dioxide powder in this slurry; Wherein titanium dioxide powder is the mixture of the Nano titanium dioxide of two kinds of different-grain diameter sizes; The mixture of the Nano titanium dioxide of two kinds of different-grain diameter sizes is that the P25 titanium dioxide powder mixes with the nanometer level titanium dioxide powder littler than P25 titanium dioxide powder according to a certain percentage, and the nanometer level titanium dioxide powder littler than P25 titanium dioxide powder is homemade titanium dioxide powder.The nanocrystalline particle diameter of homemade titanium dioxide powder is 8-16nm, and specific area is 90-100m
2/ g; The nanocrystalline average grain diameter of P25 titanium dioxide powder is 25nm, comprising the titanium dioxide granule particle size range be 20-30nm, specific area is 55m
2/ g.Existing oarse-grained Nano titanium dioxide crystal has short grained Nano titanium dioxide crystal again in this slurry.The light anode that is made by this slurry makes full use of bulky grain titanium dioxide nanocrystalline and the nanocrystalline advantage separately of small particle titanium dioxide; Short grained titanium dioxide nanocrystalline specific area is big; The absorbing dye ability is strong, and granule accumulates in the effect that can play connection between the bulky grain simultaneously, thereby improves the connectivity of light anode interior; Help the transmission of electronics, improve the mechanical strength of light anode; Oarse-grained titanium dioxide nanocrystalline interface is few, does not exist the crystal boundary potential barrier to help electric transmission, but thereby enhanced light scattering increases the optical absorption characteristics that light path realizes increasing the light anode simultaneously.Both guaranteed that the light anode had higher light capture rate, and improved the light-sensitive coloring agent adsorbance, strengthened the generation rate and the conveying capacity of photo-generated carrier, reduced the recombination process of photo-generated carrier.
Preferably, the mixture of the Nano titanium dioxide crystal of two kinds of different-grain diameters size be the P25 titanium dioxide powder with than the mixed in molar ratio of the little homemade nanometer level titanium dioxide powder of P25 titanium dioxide powder according to 1: 3～3: 1.
More preferably, the P25 titanium dioxide powder with than the mixed in molar ratio of the little homemade nanometer level titanium dioxide powder of P25 titanium dioxide powder according to 1: 2～2: 1.
The present invention relates to a kind of preparation method of light anode slurry of used by dye sensitization solar battery, this method may further comprise the steps:
(1) the nanocrystalline preparation of small particle titanium dioxide powder:
Titanium alkoxide or titanium salt are mixed with acid at normal temperatures, stir to wherein adding entry, water at normal temperature is separated; Add strong acid in the hydrolysate; Then this hydrolysate is put into and heats the reaction that is hydrolyzed in the water-bath, generate colloidal sol, the colloidal sol that generates is transferred in the autoclave reacted; With solvent centrifuge washing, drying, it is nanocrystalline promptly to obtain the small particle titanium dioxide powder with products therefrom.
(2) preparation of organic carrier
Ethyl cellulose is mixed with terpinol in proportion, and ethyl cellulose is dissolved in the terpinol, thus stir form certain viscosity organic carrier for future use.
(3) preparation of nano titania mixed crystal
Nanocrystalline and the nanocrystalline proportionally mixing of P25 titanium dioxide powder with the small particle titanium dioxide powder of step (1) preparation.
(4) preparation of organic carrier system titania slurry
The nano titania mixed crystal of step (3) preparation is joined in the ethanol, the organic carrier in the step (2) is joined in the compound of ethanol and nano titania mixed crystal, stirring and evenly mixing prepares the light anode slurry of used by dye sensitization solar battery.
Preferably; One of titanium alkoxide described in the above-mentioned steps (1) or titanium salt are: in butyl titanate, isopropyl titanate, titanium sulfate, the lactic acid titanium ammonium; One of with the acid of titanium alkoxide or titanium salt reaction be: in acetic acid, ethanedioic acid, salicylic acid, the polyacrylic acid; The acid of titanium alkoxide or titanium salt and reaction was according to 2: 1～1: 3 mixed in molar ratio, and the weight of the water of adding is titanium salt or titanium alkoxide weight 3～9 times.
More preferably, the acid of the titanium alkoxide described in the step (1) or titanium salt and reaction was according to 5: 3～3: 4 mixed in molar ratio, and the weight of the water of adding is titanium salt or titanium alkoxide weight 4～6 times.
Preferably, the time that the water at normal temperature described in the above-mentioned steps (1) is separated is 0.5h～4h, and the temperature of water-bath is 60～100 ℃ in the water-bath, and the time of hydrolysis is 0.5h～5h in the water-bath.
More preferably, the time that the water at normal temperature described in the above-mentioned steps (1) is separated is 1h～3h, and bath temperature is 70～90 ℃ in the water-bath, and the time of hydrolysis is 1.5h～3h in the water-bath.
Preferably, the temperature in the autoclave described in the above-mentioned steps (1) is 180～250 ℃, and the reaction time is 10～36h.
More preferably, the temperature in the autoclave described in the above-mentioned steps (1) is 200～230 ℃, and the reaction time is 18～34h.
Preferably, ordinary-temp hydrolysis is after the regular hour in the above-mentioned steps (1), and the strong acid that adds in the hydrolysate is nitric acid.Collosol and gel reacts products therefrom with distilled water or ethanol centrifuge washing in autoclave, dry down at 70 ℃.
Preferably, the ratio of quality and the number of copies of ethyl cellulose and terpinol is 1: 5～1: 9 in the above-mentioned steps (2), thus both stir form certain viscosity organic carrier for future use.
More preferably, the ratio of quality and the number of copies of ethyl cellulose and terpinol is 1: 6～1: 8 in the above-mentioned steps (2), thus both stir form certain viscosity organic carrier for future use.
Preferably; The small particle titanium dioxide powder that makes according to step (1) described in the above-mentioned steps (3) nanocrystalline with the P25 titanium dioxide powder nanocrystalline according to 1: 3～3: 1 mixed in molar ratio, the weight of the dispersant ethanol that adds in the step (4) is 2～5 times of nano titania mixed crystal weight.
More preferably; The small particle titanium dioxide powder that makes according to step (1) described in the above-mentioned steps (3) nanocrystalline with the P25 titanium dioxide powder nanocrystalline according to 1: 2～2: 1 mixed in molar ratio, the weight of the dispersant ethanol that adds in the step (4) is 3～4 times of nano titania mixed crystal weight.
The ratio of quality and the number of copies of the organic carrier that preferably, makes in nano titania mixed crystal described in the above-mentioned steps (4) and the above-mentioned steps (2) is 1: 2～1: 7.
The ratio of quality and the number of copies of the organic carrier that more preferably, makes in nano titania mixed crystal described in the above-mentioned steps (4) and the above-mentioned steps (2) is 1: 3～1: 5.
The invention provides light anode slurry by the used by dye sensitization solar battery of above-mentioned slurry preparation method preparation.Titanium dioxide powder in this slurry is the mixture of the Nano titanium dioxide crystal of two kinds of different-grain diameter sizes; The mixture of the Nano titanium dioxide of two kinds of different-grain diameter sizes is that the P25 titanium dioxide powder mixes with the nanometer level titanium dioxide powder littler than P25 titanium dioxide powder according to a certain percentage; The nanometer level titanium dioxide powder littler than P25 titanium dioxide powder is homemade titanium dioxide powder, and this homemade titanium dioxide powder is according to above-mentioned method preparation.The nanocrystalline particle diameter of homemade titanium dioxide powder is 8-16nm, and specific area is 90-100m
2/ g; The nanocrystalline average grain diameter of P25 titanium dioxide powder is 25nm, comprising the titanium dioxide granule particle size range be 20-30nm, specific area is 55m
2/ g.
The present invention also provides the light anode of the used by dye sensitization solar battery that uses above-mentioned smooth anode slurry preparation.
Use above-mentioned smooth anode slurry to prepare used by dye sensitization solar battery light anode; Then this light anode is docked electrode with platinum; Splash into electrolyte, be assembled into battery, promptly this DSSC comprises the light anode with the used by dye sensitization solar battery of above-mentioned pulp preparation.
Advantage of the present invention: this slurry preparation method is simple, and equipment needed thereby is simple, and the titania slurry good dispersion is filmed evenly, and nano titania slurry stability is high, and it is not stratified and do not have deposition to leave standstill the several months, is easy to preserve.With the dye sensitized solar battery anode film that nano titania slurry of the present invention is prepared, have that surfacing, specific area are big, the absorbing dye ability is strong, the space is evenly distributed, and is strong with the substrate adhesion, and optoelectronic transformation efficiency is high.The DSSC that the mixed slurry that uses the present invention to prepare is made is at 100mW/cm
2The photoelectric conversion efficiency that obtains down of simulated solar irradiation can reach 6.27%.
Improved the sunlight utilance, the charge carrier that better light conducting faster excites dyestuff to produce improves the electric transmission rate, improves photoelectric conversion rate.Improve the Fermi level and the light induced electron transmission rate of light anode, and then significantly improved open circuit voltage.Widened the absorption band of light anode to sunlight simultaneously, made the light anode in transmission electronic, self also absorbs visible light, produces light induced electron, and can make the dyestuff anode slurry of sharing the same light that better energy level matching effect is arranged.
Description of drawings
Fig. 1-P25 titanium dioxide powder nanocrystalline with the embodiment of the invention 1 in the pairing cell I-V detection of the light anode figure that makes of the slurry that is mixed with of the homemade nanometer level titanium dioxide powder littler than P25 titanium dioxide powder;
Nano titanium oxide in Fig. 2-slurry is that the pairing cell I-V of light anode of the pulp preparation of P25 titanium dioxide nanocrystalline detects figure entirely;
In Fig. 3-embodiment of the invention 1 the P25 titanium dioxide powder nanocrystalline with present embodiment in the sem photograph of mixture of the homemade nanometer level titanium dioxide powder littler than P25 titanium dioxide powder.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing and embodiment.
Embodiment 1:
Take by weighing the 34g butyl titanate, to wherein adding 6g acetic acid, fully stirring mixes butyl titanate and acetic acid; And then to the water that wherein adds 170ml, water at normal temperature is separated 1.5h, and hydrolysis takes place butyl titanate especially easily; Reunite, generate oarse-grained titanium dioxide, acetic acid can suppress tetrabutyl titanate hydrolysis; The tetrabutyl titanate hydrolysis reaction speed is slowed down, generate short grained homodisperse hydrolysate.In this hydrolysate, add nitric acid 5ml, nitric acid can make particle diminish, and disperses more even.This hydrolysate put in 80 ℃ the water-bath, reaction 2h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 230 ℃ are reacted 24h down, and the product that hydro-thermal reaction is obtained makes water centrifuge washing, 70 ℃ of dryings obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 94m
2/ g.
The P25 titanium dioxide powder that takes by weighing 3.6g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 3.6g, and both ground and mixed are even, in mixture, adds ethanol 24ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 4g takes by weighing the terpinol of 32g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
The P25 titanium dioxide powder nanocrystalline with the embodiment of the invention 1 in the sem photograph of mixture of the homemade nanometer level titanium dioxide powder littler than P25 titanium dioxide powder as shown in Figure 3; Big particle majority is that the P25 titanium dioxide powder is nanocrystalline among this figure, and little particle majority is that homemade titanium dioxide powder is nanocrystalline.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency that this membrane electrode is formed.
The P25 titanium dioxide powder that obtains in the above-mentioned steps nanocrystalline with present embodiment in the pairing cell I-V detection of the light anode figure that makes of the slurry that is mixed with of the homemade nanometer level titanium dioxide powder littler than P25 titanium dioxide powder as shown in Figure 1; Can find out that from test result the short-circuit current density of battery is 13.58mA/cm
2, open circuit voltage is 0.64V, and fill factor, curve factor is 71.42%, and photoelectric conversion efficiency is 6.27%.
Comparative Examples
The particle diameter of P25 titanium dioxide powder is 25nm, and specific area is 55m
2/ g.The P25 titanium dioxide powder that takes by weighing 7.2g is nanocrystalline, adds ethanol 24ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 4g takes by weighing the terpinol of 32g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency that this membrane electrode is formed.
As shown in Figure 2 in the above-mentioned steps by the pairing cell I-V detection of the light anode figure of the nanocrystalline pulp preparation that makes of P25 titanium dioxide powder, can find out that from test result the short-circuit current density of battery is 12.63mA/cm
2, open circuit voltage is 0.61V, and fill factor, curve factor is 64.92%, and photoelectric conversion efficiency is 5.28%.
Embodiment 2:
Take by weighing the 28.8g isopropyl titanate, to wherein adding the 5.16g polyacrylic acid, fully stirring mixes isopropyl titanate and polyacrylic acid, and then to the water that wherein adds 260ml, water at normal temperature is separated 4h.In this hydrolysate, add nitric acid 5ml, nitric acid can make particle diminish, and disperses more even.This hydrolysate put in 100 ℃ the water-bath, reaction 5h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 210 ℃ are reacted 36h down, and the product that hydro-thermal reaction is obtained makes water centrifuge washing, 70 ℃ of dryings obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 90m
2/ g.
The P25 titanium dioxide powder that takes by weighing 14g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 6g, and both ground and mixed are even, in mixture, adds ethanol 50ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 5g takes by weighing the terpinol of 35g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 3:
Take by weighing 29.4g lactic acid titanium ammonium, to the water that wherein adds 90ml, water at normal temperature is separated 1h.This hydrolysate put in 90 ℃ the water-bath, reaction 1.5h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 220 ℃ are reacted 22h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 95m
2/ g.
The P25 titanium dioxide powder that takes by weighing 5.32g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 7.98g, and both ground and mixed are even, in mixture, adds 20ml ethanol as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 4g takes by weighing the terpinol of 36g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 4:
Take by weighing the 24g titanium sulfate, to wherein adding 8g acetic acid, fully stirring mixes titanium sulfate and acetic acid, and then to the water that wherein adds 150ml, water at normal temperature was separated 2.5 hours.This hydrolysate put in 60 ℃ the water-bath, reaction 2h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 180 ℃ are reacted 18h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 100m
2/ g.
The P25 titanium dioxide powder that takes by weighing 1.5g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 4.5g, and both ground and mixed are even, in mixture, adds ethanol 32ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 7g takes by weighing the terpinol of 35g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 5:
Take by weighing the 34g butyl titanate, to wherein adding the 27g ethanedioic acid, fully stirring mixes butyl titanate and ethanedioic acid, and then to the water that wherein adds 170ml, water at normal temperature is separated 1h.In this hydrolysate, add nitric acid 5ml, nitric acid can make particle diminish, and disperses more even.This hydrolysate put in 80 ℃ the water-bath, reaction 3h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 250 ℃ are reacted 12h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 92m
2/ g.
The P25 titanium dioxide powder that takes by weighing 3.5g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 7g, and both ground and mixed are even, in mixture, adds ethanol 24ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 6g takes by weighing the terpinol of 36g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 6:
Take by weighing 29.4g lactic acid titanium ammonium, to the water that wherein adds 210ml, water at normal temperature was separated 0.5 hour.This hydrolysate put in 70 ℃ the water-bath, reaction 1h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 240 ℃ are reacted 24h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 96m
2/ g.
The P25 titanium dioxide powder that takes by weighing 7.98g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 5.32g, and both ground and mixed are even, in mixture, adds ethanol 50ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 5g takes by weighing the terpinol of 35g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 7:
Take by weighing the 28.8g isopropyl titanate, to wherein adding 3g acetic acid, fully stirring mixes isopropyl titanate and acetic acid, and then to the water that wherein adds 120ml, water at normal temperature is separated 1h.In this hydrolysate, add nitric acid 5ml, nitric acid can make particle diminish, and disperses more even.This hydrolysate put in 80 ℃ the water-bath, reaction 2h forms colloidal sol.The colloidal sol that generates is transferred in the autoclave, and 200 ℃ are reacted 12h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder, and the particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 94m
2/ g.
The P25 titanium dioxide powder that takes by weighing 6g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 3g, and both ground and mixed are even, in mixture, adds ethanol 18ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 4g takes by weighing the terpinol of 32g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
Embodiment 8:
Take by weighing the 24g titanium sulfate, to wherein adding the 8.3g salicylic acid, fully stirring mixes titanium sulfate and salicylic acid; And then to the water that wherein adds 140ml, water at normal temperature was separated 3.5 hours, and dispersed with stirring is even; Directly transfer in the autoclave, 190 ℃ are reacted 10h down, and the product that hydro-thermal reaction is obtained uses ethanol centrifuge washing, 70 ℃ of dryings to obtain required powder; The particle diameter of this homemade titanium dioxide powder is 8～16nm, and specific area is 93m
2/ g.
The P25 titanium dioxide powder that takes by weighing 6.3g is nanocrystalline nanocrystalline with the homemade small particle titanium dioxide powder of the above-mentioned reactions step of 2.1g, and both ground and mixed are even, in mixture, adds ethanol 32ml as dispersant.The ethyl cellulose of 200Pa.s that takes by weighing 6g takes by weighing the terpinol of 36g as bonding agent, and the ethyl cellulose that weighs up is mixed with terpinol, and ethyl cellulose is dissolved in the terpinol, thereby stirs the organic carrier that forms certain viscosity.This organic carrier is joined in the compound of above-mentioned ethanol and nano titania mixed crystal, obtain the light anode slurry that needs.
Above-mentioned light anode slurry stirred after one hour; This slurry is filmed on electro-conductive glass; With the electro-conductive glass that coats film in Muffle furnace 450 ℃ the calcining 30 minutes, the thickness on the cool to room temperature electro-conductive glass obtains the light anode of dye sensitized nano crystal salar battery 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)] solution 24h, 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 battery, its efficient of test under xenon lamp simulated solar light source.The composition of electrolyte is 1MLiI, 0.1MI2, and the 0.5M4-butyl-pyridinium, solvent is butyronitrile and propene carbonate (PC) (volume ratio is 1: 1).Survey efficient institute use xenon lamp simulated solar irradiation, light intensity is 100mW/cm
2(measuring light intensity with the standard silicon photodiode) under this light intensity, records the cell photoelectric conversion efficiency 5.28～6.27% that this membrane electrode is formed.
It is 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 the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (10)
1. the light anode slurry of a used by dye sensitization solar battery; Include ethyl cellulose, terpinol, titanium dioxide powder in this slurry; It is characterized in that titanium dioxide powder is the mixture of the Nano titanium dioxide of two kinds of different-grain diameters size, the mixture of the Nano titanium dioxide of two kinds of different-grain diameter sizes be the P25 titanium dioxide powder with than the mixed in molar ratio of the little homemade nanometer level titanium dioxide powder of P25 titanium dioxide powder according to 1: 3～3: 1.
2. the light anode slurry of a kind of used by dye sensitization solar battery according to claim 1, the mixture that it is characterized in that the Nano titanium dioxide of two kinds of different-grain diameters sizes be the P25 titanium dioxide powder with than the mixed in molar ratio of the little homemade nanometer level titanium dioxide powder of P25 titanium dioxide powder according to 1: 2～2: 1.
3. the light anode slurry of a kind of used by dye sensitization solar battery according to claim 1 and 2, the particle diameter that it is characterized in that homemade titanium dioxide powder is 8～16nm, specific area is 90～100m
2/ g.
4. the preparation method of the light anode slurry of a used by dye sensitization solar battery is characterized in that this method may further comprise the steps:
(1) the nanocrystalline preparation of small particle titanium dioxide powder
Titanium alkoxide or titanium salt are mixed with acid at normal temperatures, stir to wherein adding entry, water at normal temperature is separated; Add strong acid in the hydrolysate; Then this hydrolysate is put into and heats the reaction that is hydrolyzed in the water-bath, generate colloidal sol, the colloidal sol that generates is transferred in the autoclave reacted; With solvent centrifuge washing, drying, it is nanocrystalline promptly to obtain homemade small particle titanium dioxide powder with products therefrom.
(2) preparation of organic carrier
Ethyl cellulose is mixed with terpinol in proportion, and ethyl cellulose is dissolved in the terpinol, thus stir form certain viscosity organic carrier for future use.
(3) preparation of nano titania mixed crystal
Nanocrystalline and the nanocrystalline proportionally mixing of P25 titanium dioxide powder with the small particle titanium dioxide powder of step (1) preparation.
(4) preparation of organic carrier system titania slurry
The nano titania mixed crystal of step (3) preparation is joined in the ethanol, the organic carrier in the step (2) is joined in the compound of ethanol and nano titania mixed crystal, stirring and evenly mixing prepares the light anode slurry of used by dye sensitization solar battery.
5. the preparation method of the light anode slurry of used by dye sensitization solar battery according to claim 4; One of it is characterized in that titanium alkoxide described in the step (1) or titanium salt are: in butyl titanate, isopropyl titanate, titanium sulfate, the lactic acid titanium ammonium; One of with the acid of titanium alkoxide or titanium salt reaction be: in acetic acid, ethanedioic acid, salicylic acid, the polyacrylic acid; The acid of titanium alkoxide or titanium salt and reaction was according to 2: 1～1: 3 mixed in molar ratio; The strong acid that adds in the hydrolysate is nitric acid, and the weight of the water of adding is titanium salt or titanium alkoxide weight 3～9 times; Preferably the acid of the titanium alkoxide described in the step (1) or titanium salt and reaction was according to 5: 3～3: 4 mixed in molar ratio, and the weight of the water of adding is titanium salt or titanium alkoxide weight 4～6 times.
6. the preparation method of the light anode slurry of used by dye sensitization solar battery according to claim 4; It is characterized in that the time that the water at normal temperature described in the step (1) is separated is 0.5h～4h; The temperature of water-bath is 60-100 ℃ in the water-bath, and the time of hydrolysis is 0.5h-5h in the water-bath, and preferably the time of separating of the water at normal temperature described in the step (1) is 1h～3h; Bath temperature is 70～90 ℃ in the water-bath, and the time of hydrolysis is 1.5h-3h in the water-bath.
7. the preparation method of the light anode slurry of used by dye sensitization solar battery according to claim 4; It is characterized in that the temperature in the autoclave described in the step (1) is 180-250 ℃; Reaction time is 10-36h; Preferably the temperature in the autoclave described in the step (1) is 200-230 ℃, and the reaction time is 18-34h.
8. the preparation method of the light anode slurry of used by dye sensitization solar battery according to claim 4; The ratio of quality and the number of copies that it is characterized in that middle ethyl cellulose of step (2) and terpinol is 1: 5～1: 9; Small particle titanium dioxide powder that makes according to step (1) described in the step (3) and P25 titanium dioxide powder according to 1: 3-3: 1 mixed in molar ratio; The weight of the dispersant ethanol that adds in the step (4) is 2～5 times of nano titania mixed crystal weight, and the ratio of quality and the number of copies of the organic carrier that makes in nano titania mixed crystal and the step (2) in the step (4) is 1: 2～1: 7; Preferably the mass fraction ratio of ethyl cellulose and terpinol is 1: 6～1: 8 in the step (2); The titanium dioxide granule powder that makes according to step (1) described in the step (3) nanocrystalline with the P25 titanium dioxide powder nanocrystalline according to 1: 2-2: 1 mixed in molar ratio; The weight of the dispersant ethanol that adds in the step (4) is 3～4 times of nano titania mixed crystal weight, and the ratio of quality and the number of copies of the organic carrier that makes in nano titania mixed crystal and the step (2) in the step (4) is 1: 3～1: 5.
9. the light anode of a used by dye sensitization solar battery is characterized in that comprising the light anode of use according to the dye sensitization of solar light anode slurry preparation of the arbitrary described method preparation of claim 4-8.
10. DSSC is characterized in that comprising the light anode of the described used by dye sensitization solar battery of claim 9.
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| CN2011104577298A CN102446632B (en) | 2011-12-31 | 2011-12-31 | Optical anode slurry for dye-sensitized solar cell and preparation method thereof as well as optical anode for dye-sensitized solar cell and dye-sensitized solar cell |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674453A (en) * | 2012-06-06 | 2012-09-19 | 奇瑞汽车股份有限公司 | Titanium dioxide and preparation method thereof, photoanode slurry and preparation method thereof as well as solar battery |
| CN102815748A (en) * | 2012-08-24 | 2012-12-12 | 奇瑞汽车股份有限公司 | Titanium dioxide material, preparation method thereof, and dye sensitization solar cell |
| CN102938327A (en) * | 2012-12-04 | 2013-02-20 | 奇瑞汽车股份有限公司 | Doped titanium dioxide and preparation method thereof and dye-sensitized solar cell photo-anode and cell prepared from same |
| CN103227055A (en) * | 2013-04-28 | 2013-07-31 | 奇瑞汽车股份有限公司 | Photoanode and preparation method thereof, and dye-sensitized solar cell |
| WO2016104313A1 (en) * | 2014-12-26 | 2016-06-30 | 御国色素株式会社 | Dispersion liquid for formation of semiconductor electrode layer, and semiconductor electrode layer |
| CN112876906A (en) * | 2021-01-12 | 2021-06-01 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot scattering slurry, color film substrate, preparation method of color film substrate and display device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101567268A (en) * | 2009-06-01 | 2009-10-28 | 彩虹集团公司 | Method for preparing ternary two-layer titanium dioxide film |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101567268A (en) * | 2009-06-01 | 2009-10-28 | 彩虹集团公司 | Method for preparing ternary two-layer titanium dioxide film |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674453A (en) * | 2012-06-06 | 2012-09-19 | 奇瑞汽车股份有限公司 | Titanium dioxide and preparation method thereof, photoanode slurry and preparation method thereof as well as solar battery |
| CN102815748A (en) * | 2012-08-24 | 2012-12-12 | 奇瑞汽车股份有限公司 | Titanium dioxide material, preparation method thereof, and dye sensitization solar cell |
| CN102938327A (en) * | 2012-12-04 | 2013-02-20 | 奇瑞汽车股份有限公司 | Doped titanium dioxide and preparation method thereof and dye-sensitized solar cell photo-anode and cell prepared from same |
| CN102938327B (en) * | 2012-12-04 | 2016-05-11 | 奇瑞汽车股份有限公司 | Dye-sensitized solar cell anode, battery prepared by titanium dioxide of doping and preparation method thereof, this material |
| CN103227055A (en) * | 2013-04-28 | 2013-07-31 | 奇瑞汽车股份有限公司 | Photoanode and preparation method thereof, and dye-sensitized solar cell |
| CN103227055B (en) * | 2013-04-28 | 2017-02-22 | 奇瑞汽车股份有限公司 | Photoanode and preparation method thereof, and dye-sensitized solar cell |
| WO2016104313A1 (en) * | 2014-12-26 | 2016-06-30 | 御国色素株式会社 | Dispersion liquid for formation of semiconductor electrode layer, and semiconductor electrode layer |
| JPWO2016104313A1 (en) * | 2014-12-26 | 2018-09-13 | 御国色素株式会社 | Dispersion liquid for forming semiconductor electrode layer and semiconductor electrode layer |
| CN112876906A (en) * | 2021-01-12 | 2021-06-01 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot scattering slurry, color film substrate, preparation method of color film substrate and display device |
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