CN100583463C - Production method for titanium oxide coating material in dye sensitized solar battery - Google Patents
Production method for titanium oxide coating material in dye sensitized solar battery 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 147
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 94
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000000084 colloidal system Substances 0.000 claims abstract description 58
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 24
- 239000001856 Ethyl cellulose Substances 0.000 claims description 21
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical group CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 21
- 229920001249 ethyl cellulose Polymers 0.000 claims description 21
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 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 claims description 20
- 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 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 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 11
- 238000010792 warming Methods 0.000 claims description 11
- 238000000875 high-speed ball milling Methods 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 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 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- -1 titanium alkoxide Chemical class 0.000 abstract description 4
- 206010070834 Sensitisation Diseases 0.000 abstract description 3
- 230000008313 sensitization Effects 0.000 abstract description 3
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 6
- 239000002159 nanocrystal Substances 0.000 description 6
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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 present invention provides a preparation method of titania coating materials applied to the dye sensitization solar battery, which is characterized in that organic titanium alkoxide is adopted as the predecessor body, the colloid of TiO2 that is stably distributed is prepared through the hydrolysis reaction of the organic titanium alkoxide. Organic polybasic acid is added into the colloid of TiO2 to adjust the pH value to be the subacidity (5.5-6.5), the organic residual substances in the colloid of TiO2 is filtered and removed by washing with vast organic solvent. Appropriate amount of industrial viscous agent is added into the clean TiO2 colloid after being washed to be grinded and mixed uniformly at a high speed so as to produce the titania coating material of the dye sensitization solar battery. The present invention has the obvious advantages of simple process, stable quality and friendly environment, and is a method that can be applied to prepare the titania coating material in large scale.
Description
Technical field
The present invention relates to the production method for titanium oxide coating material in the DSSC, belong to field of energy source materials.
Background technology
Since this century the nineties, it is found that DSSC (DSSCs) is at solar energy development with the great potential aspect utilizing.With respect to normally used crystal silicon solar energy battery, the with low cost and manufacture craft of DSSC is simple, has special advantages in the research of promoting solar energy with aspect utilizing.As a new technology that faces the future, employed nanometer porous titanium oxide active layer only has tens of microns thickness in the DSSC, on principle, this will make the application that DSSC is applicable to much needs high degree of flexibility, such as hull cell of flexible substrates etc.In DSSC, be subjected to supper-fast light induced electron that light activated light-sensitive coloring agent produces and inject the conduction band of titanium oxide and photohole is conducted to current collector through titanium oxide, thereby finish the overall process that light-electricity is changed in subsequently dyestuff regenerative process.In this course, the titanium oxide active coating is a kind of charge-conduction material of key, and obviously, preparing high-quality titanium oxide coating material is an importance of developing in the DSSC.
At present, the method for preparing the nano-titanium oxide coating layer material mainly contains sol-gel process, magnetron sputtering method and hydrolytic precipitation method etc.Wherein, the nano-titanium oxide coating layer of sol-gel process preparation has very high specific area, and easily absorbing dye has higher efficient.The general silk screen print method that adopts is coated on substrate surface with nano-titanium oxide colloidal sol more, its advantage is a process stabilizing, carrying out large tracts of land easily films, the film that forms is more even, and can control thickness, the characteristics that possess suitable suitability for industrialized production are inexorable trends of following preparation method of solar battery.But, the nano-titanium oxide colloid of sol-gel process preparation also exists degree of crystallinity relatively poor, the organic stabilizer that adds in organic product after the shortcoming that organic impurity content is higher, particularly organic titanium hydrolysis of alkoxide and the course of reaction has had a strong impact on the quality of forming film of silk screen printing.
Chinese invention patent (publication number CN1458194) discloses a kind of ultraviolet light does not have the titanium oxide sol coating that shadow glue and titania powder are mixed and made into, but the commercial oxidation ti powder exists particle diameter bigger, secondary agglomeration seriously causes the shortcoming of particle size distribution broad, thereby has influenced the unique advantage of nanometer size effect in opto-electronic conversion.Chinese patent (publication number CN1623907) discloses the method for preparing titania solution, titanium dioxide is dissolved in hydrogenperoxide steam generator has prepared the amorphous titania gel.It is the method for feedstock production blue and white transparent titania colloidal sol that Chinese patent (publication number CN1962459) discloses a kind of titanium tetrachloride, titanium sulfate or butyl titanate of adopting.The prepared nano-TiO of the above-mentioned method of enumerating
2There is the problem that the titanium oxide particle diameter is big, crystallization is incomplete and be not suitable for silk-screen printing technique respectively in colloidal sol.The titanium oxide coating material that is used for DSSC for preparing among the present invention has degree of crystallinity height, crystallite dimension is little and quality of forming film is high advantage, and technology is simple, and is with low cost, is suitable for large-scale production.
Summary of the invention
The invention provides the preparation method of titanium oxide coating material in the DSSC.This method uses the organic titanium alkoxide to be presoma, prepares the anatase phase oxidation titanium colloid of stable dispersion by the hydrolysis of organic titanium alkoxide.Titanium oxide quality percentage composition is 10-20% in this colloid, and titanium oxide grain is of a size of 5-30nm, and principal phase is the anatase phase.In titanium oxide colloid, add the organic multicomponent acid for adjusting pH to faintly acid (5.5-6.5) back washing and filtering or directly carry out washing and filtering to remove organic residue matter wherein with a large amount of organic solvents.Add the appropriate amount of industrial adhesion agent in the titanium oxide colloid of cleaning fully, the high speed ball milling mixes, and makes the titanium oxide coating material that is applicable to DSSC.This method has that technology is simple, obvious advantage such as steady quality and environmental friendliness, is a kind of method that can the scale preparation titanium oxide coating material.
The present invention implements like this: the raw material that uses is tetrabutyl titanate, isopropyl titanate, ethanol, citric acid, ethyl cellulose and terpinol etc., can be with any one preparation in following two kinds of methods:
First kind of preparation method:
(1) obtain solution A at first: organic titanate is joined in the ethanolic solution, stir the ethanolic solution of the organic titanate that is mixed with homogeneous transparent through brute force; Wherein the volume ratio of organic titanate and ethanol is 1: 2-1: 3; Described organic titanate is tetrabutyl titanate or isopropyl titanate;
(2) preparation sol B: the organic titanate solution of the homogeneous transparent of step (1) preparation is slowly splashed in a large amount of pure water, powerfully simultaneously stir the reaction that is hydrolyzed, form white anatase phase oxidation titanium colloid; Wherein pure water compares greater than 20 with the organic titanate liquor capacity;
(3) titanium oxide colloid with step (2) is warming up to 80-90 ℃, and insulation 20-24h adds organic multicomponent acid brute force then and stirs, to regulate the faintly acid of pH value to 5.5-6.5; Described organic multicomponent acid including but not limited in citric acid, oxalic acid, acetate and the ethanedioic acid one or more;
(4) for several times, be neutral, obtain white filter cake C to the filter liquor pH value with the pure water filtration washing; And with 60 ℃ of-70 ℃ of vacuum dryings of resulting white filter cake, the oven dry back adds industrial adhesion agent in the white loose powder that obtains, described industrial adhesion agent is an ethyl cellulose, the adding form is the ethanolic solution of ethyl cellulose, the mass ratio 1 of ethyl cellulose and titanium oxide: 1-5: 1, add terpinol after mixing again; The high speed ball milling mixes and obtains faint yellow titanium oxide colloid D;
(5) the faint yellow titanium oxide colloid that step (4) is obtained, the lower ethanol of boiling point is removed in decompression distillation, thereby obtains the high viscosity titanium oxide coating material of steady concentration.
Second kind of preparation method:
(1) obtain solution A at first: organic titanate is joined in the ethanolic solution, stir the ethanolic solution of the organic titanate that is mixed with homogeneous transparent through brute force; Wherein the volume ratio of organic titanate and ethanol is 1: 2-1: 3; Described organic titanate is tetrabutyl titanate or isopropyl titanate;
(2) preparation sol B: the organic titanate solution of the homogeneous transparent of step (1) preparation is slowly splashed in a large amount of pure water, powerfully simultaneously stir the reaction that is hydrolyzed, form white anatase phase oxidation titanium colloid; Wherein pure water and organic titanate volume ratio are greater than 20;
(3) titanium oxide colloid with step (2) is warming up to 80-90 ℃, insulation 20-24h, directly adopt a large amount of organic solvents to carry out washing and filtering to remove organic substance residues material wherein, the organic solvent that is adopted is including but not limited to one or more mixed solvents such as methyl alcohol, ethanol, acetone, benzene and toluene, and the volume ratio of employed organic solvent and organic titanate is 20: 1-30: 1;
(4) vacuum drying under 60 ℃ of-70 ℃ of temperature of the white filter cake C behind the washing and filtering, the ethanolic solution that adds ethyl cellulose after the oven dry after crushed, wherein, the mass ratio of ethyl cellulose and titanium oxide is 1: 1-5: 1, add terpinol after mixing again, obtain faint yellow titanium oxide colloid D after high speed is ground mixing;
(5) the faint yellow titanium oxide colloid that step (4) is made, the lower ethanol of boiling point is removed in decompression distillation, thereby obtains the high viscosity titanium oxide coating material of specific concentrations.
The preparation method of titanium oxide coating material in the DSSC provided by the invention is characterized in:
(1) prepare the uniform anatase phase oxidation of particle size distribution titanium colloidal sol with tetrabutyl titanate or isopropyl titanate as the hydrolysis of titanium source, wherein pure water and tetrabutyl titanate volume ratio are greater than 20.
(2) in order to remove organic impurities in the titanium oxide sol, add a certain amount of organic multicomponent acid, by breakdown of emulsion under the uniform temperature and dispergation process, make titanium oxide grain generation flocculation sediment, thereby the organic impurities that is easy to dissociate is out removed with the pure water washing.
(3) in order to remove organic impurities in the titanium oxide sol, also can carry out washing and filtering to titanium oxide sol by using a large amount of organic solvents, the organic solvent that is adopted is including but not limited to one or more mixture such as methyl alcohol, ethanol, acetone, benzene and toluene.
(4) will remove the ethanolic solution that titanium oxide colloid oven dry back behind the organic impurities adds ethyl cellulose, and add the terpinol of 200mL after mixing again, the high speed ball milling mixes.
(5) the lower ethanol of boiling point is removed in the titanium oxide colloid decompression distillation after the high speed ball milling is mixed, and obtains the high viscosity titanium oxide coating material of specific concentrations.
(6) the titanium oxide principal crystalline phase is the anatase phase in the titanium oxide coating material of this method preparation, and crystallite dimension is 5-30nm, TiO
2The quality percentage composition be 10%-20%, good dispersion is applicable to the DSSC that processability is good.
(7) the experimental technique route of this method is simple, and operation is convenient.Whole technical process need not HTHP, unprotect atmosphere, and technology is succinct, and reaction is a kind of efficient quick fast, the eco-friendly method for preparing titanium oxide coating material in the DSSC.
(8) embodiment 1-3 adopts different organic titanate (embodiment 1,2) and the prepared titanium oxide coating materials of two kinds of preparation methods (embodiment 1,3) to be applicable to used by dye sensitization solar battery in the embodiment, its conversion efficiency is greater than 8%, reach as high as 8.5%, and embodiment 4-6 as a comparison, do not adopt method provided by the invention fully, the photoelectric conversion rate that then uses prepared titanium oxide coating material to make DSSC reduces greatly, and minimum only is 4.3%.Thereby reflect fully that from a side method provided by the invention has substantive distinguishing features and obvious improvement.
Description of drawings
Fig. 1. original nano-crystal titanium oxide colloid TEM photo
Fig. 2. the XRD spectra of original nano-crystal titanium oxide colloid
Fig. 3. the SEM photo of original nano-crystal titanium oxide colloid silk screen printing film
Fig. 4. the titanium oxide colloid TEM photo after the organic multicomponent acid treatment
Fig. 5. the SEM photo of organic multicomponent acid treatment rear oxidation titanium colloid silk screen printing film
Fig. 6. ethanol-benzene mixed liquor washing and filtering rear oxidation titanium colloid TEM photo
Fig. 7. the SEM photo of ethanol-benzene mixed liquor washing and filtering rear oxidation titanium colloid silk screen printing film
Fig. 8. the titanium oxide colloid TEM photo after the nitric acid treatment
Embodiment
With the embodiment of following indefiniteness, in conjunction with the accompanying drawings substantive distinguishing features of the present invention and marked improvement are further elaborated:
Embodiment 1
Obtain solution A at first: the tetrabutyl titanate of 100mL is added the ethanolic solution of 200mL, and brute force stirs and obtains light yellow transparent solution.Solution A is slowly splashed in the pure water of 2000mL, powerful simultaneously the stirring forms the milky sol B.Sol B is warming up to 90 ℃ of insulation 24h, adds 3M citric acid 200mL, after brute force stirs, with the pure water filtration washing for several times, be neutral, obtain white filter cake C to filter liquor pH value.With filter cake C in 60 ℃ of vacuum dryings, the white loose powder that obtains after the oven dry adds the ethanolic solution of ethyl cellulose, wherein the weight ratio of ethyl cellulose and titanium oxide is 2: 1, adds the terpinol of 200mL after mixing again, and the high speed ball milling mixes and obtains faint yellow titanium oxide colloid D.The lower ethanol of boiling point is removed in titanium oxide colloid D decompression distillation, obtained the high viscosity titanium oxide coating material of specific concentrations.Use the photoelectric conversion efficiency of the DSSC of its preparation to be up to 8.5%.Fig. 1 can see the titanium oxide grain size less than 10nm for sol B is warming up to the TEM photo of original nano-crystal titanium oxide colloid behind 90 ℃ of insulation 24h, has wrapped up large amount of organic matter around the crystal grain.Fig. 2 is the XRD spectra of original nano-crystal titanium oxide colloid, and as seen from the figure, the principal phase of titanium oxide crystal is the anatase phase.Fig. 3 be original nano-crystal titanium oxide colloid through the SEM of silk screen printing rear film photo, can see that because the existence of large amount of organic matter makes that the crystal grain dispersiveness is relatively poor in the titania coating cracking, agglomeration are obvious.Fig. 4 is the TEM photo of organic multicomponent acid treatment rear oxidation titanium colloid, can see that the titanium oxide grain size obviously do not grow up, and grain edges is clear, almost can't see organic substance and exists.Fig. 5 is the SEM photo of organic multicomponent acid treatment rear oxidation titanium colloid silk screen printing film, can find that titan oxide particles is clearly visible in this film, cracking, agglomeration obviously reduce, and the formation tridimensional network that interlinks between particle helps the absorption utilization of light-sensitive coloring agent.
Embodiment 2
Obtain solution A at first: the isopropyl titanate of 100mL is added the ethanolic solution of 300mL, and brute force stirs and obtains clear solution.Solution A is slowly splashed in the pure water of 3000mL, powerful simultaneously the stirring forms the milky sol B.Sol B is warming up to 90 ℃ of insulation 24h, adds 3M acetate 300mL, after brute force stirs, with the pure water filtration washing for several times, be neutral, obtain white filter cake C to filter liquor pH value.With filter cake C in 60 ℃ of vacuum dryings, the white loose powder that obtains after the oven dry adds the ethanolic solution of ethyl cellulose, wherein the weight ratio of ethyl cellulose and titanium oxide is 2: 1, adds the terpinol of 200mL after mixing again, and the high speed ball milling mixes and obtains faint yellow titanium oxide colloid D.The lower ethanol of boiling point is removed in titanium oxide colloid D decompression distillation, obtained the high viscosity titanium oxide coating material of specific concentrations.Use isopropyl titanate obviously not distinguish as among the titanium oxide coating material of presoma preparation and the embodiment 1.
Embodiment 3
Obtain solution A at first: the tetrabutyl titanate of 100mL is added the ethanolic solution of 200mL, and brute force stirs and obtains light yellow transparent solution.Solution A is slowly splashed in the pure water of 2000mL, powerful simultaneously the stirring forms the milky sol B.Sol B is warming up to 90 ℃ of insulation 24h, directly adopts ethanol-benzene mixed liquor washing and filtering several of 2000mL, obtain white filter cake C.With filter cake C in 60 ℃ of vacuum dryings, the caking material that obtains after the oven dry is through pulverizing the ethanolic solution that the back adds ethyl cellulose, wherein the weight ratio of ethyl cellulose and titanium oxide is 2: 1, the terpinol that adds 200mL after mixing again, high speed ball milling mix and obtain faint yellow titanium oxide colloid D.The lower ethanol of boiling point is removed in titanium oxide colloid D decompression distillation, obtained the titanium oxide coating material of specific concentrations.Use the photoelectric conversion efficiency of the DSSC of its preparation to reach as high as 8.1%.Fig. 6 is process ethanol-benzene mixed liquor washing and filtering rear oxidation titanium colloid TEM photo, can see that organic substance obviously reduces in the colloid, grain edges is also more clearly, but has certain agglomeration, and this makes that the titanium oxide colloid caking phenomenon after the washing is more serious.Fig. 7 is the SEM photo of ethanol-benzene mixed liquor washing and filtering rear oxidation titanium colloid silk screen printing film, can see that the titania coating film quality is better than primary sample, and particle size is less than 30nm.
Embodiment 4
Obtain solution A at first: the tetrabutyl titanate of 100mL is added the ethanolic solution of 200mL, and brute force stirs and obtains light yellow transparent solution.Solution A is slowly splashed in the pure water of 2000mL, powerful simultaneously the stirring forms the milky sol B.Sol B is warming up to 90 ℃ of insulation 24h, adds 3M nitric acid 200mL, after brute force stirs, generate milky pulpous state material, can not carry out filtration washing, illustrate under the effect of inorganic acid, titan oxide particles generation peptization phenomenon, crystallization degree reduces.Fig. 8 is the TEM photo of nitric acid treatment rear oxidation titanium colloid, can see that the titanium oxide major part is dissolved, only has a spot of crystal region, and this will make the photoelectric conversion efficiency of dye-sensitized cell reduce greatly.
Embodiment 5
Obtain solution A at first: the tetrabutyl titanate of 100mL is added the ethanolic solution of 200mL, and brute force stirs and obtains light yellow transparent solution.Solution A is slowly splashed in the pure water of 2000mL, powerful simultaneously the stirring forms the milky sol B.Sol B is warming up to 90 ℃ of insulation 24h, adds 3M citric acid 200mL, after brute force stirs, with the pure water filtration washing for several times, be neutral, obtain white filter cake C to filter liquor pH value.With filter cake C in 60 ℃ of vacuum dryings, the white loose powder that obtains after the oven dry adds the ethanolic solution of polyvinyl alcohol, wherein the weight ratio of polyvinyl alcohol and titanium oxide is 2: 1, the terpinol that adds 200mL after mixing again, obtain the relatively poor white thickness slurry of rheological property after the high speed ball milling mixes, with the photoelectric conversion efficiency of the dye-sensitized cell of its preparation only up to 5.2%.This explanation selects suitable industrial adhesion agent extremely important for the photoelectric properties that improve titanium oxide coating material.
Embodiment 6
Directly take by weighing the ethanolic solution of certain amount of nano level titanium dioxide powder (German Degussa P-25) adding ethyl cellulose, wherein the weight ratio of ethyl cellulose and titanium oxide is 2: 1, add a certain amount of terpinol after mixing again, the high speed ball milling mixes and obtains the milky titanium oxide colloid.The lower ethanol of boiling point is removed in this titanium oxide colloid decompression distillation, obtained certain density titanium oxide coating material.Make DSSC after silk screen printing, its photoelectric conversion efficiency is up to 4.3%, is starkly lower than the titanium oxide coating material for preparing among the present invention.Illustrate that the present invention adopts the titanium oxide colloid crystallite dimension that makes behind the organic titanium hydrolysis of alkoxide less, specific area is bigger, and surface active groups is more, thereby is easy to improve in conjunction with light-sensitive coloring agent the opto-electronic conversion ability of battery more.
Claims (7)
1, the coating of titanium dioxide material preparation method in the DSSC is characterized in that with tetrabutyl titanate or isopropyl titanate be presoma, prepares the anatase phase oxidation titanium colloid of stable dispersion by the hydrolysis of presoma
In titanium oxide colloid, add the organic multicomponent acid for adjusting pH and be after the 5.5-6.5 faintly acid washing and filtering or directly carry out washing and filtering to remove organic residue matter wherein with a large amount of organic solvents; At the TiO that cleans fully
2Add the appropriate amount of industrial adhesion agent in the colloid, the high speed ball milling mixes, and makes the coating of titanium dioxide material that is applicable to DSSC.
2, profit requires coating of titanium dioxide preparation methods in 1 described a kind of DSSC, it is characterized in that adopting in following two kinds of methods any:
First kind of preparation method:
A) tetrabutyl titanate or isopropyl titanate are joined in the ethanolic solution, be mixed with the tetrabutyl titanate of homogeneous transparent or the ethanolic solution of isopropyl titanate through stirring; Wherein the volume ratio of tetrabutyl titanate or isopropyl titanate and ethanol is 1: 2-1: 3;
B) tetrabutyl titanate of the homogeneous transparent that step a is prepared or the ethanolic solution of isopropyl titanate splash in a large amount of pure water, and brute force stirs the reaction that is hydrolyzed simultaneously, forms white anatase phase oxidation titanium colloid; Wherein the volume ratio of pure water and tetrabutyl titanate or titanium isopropoxide solution is greater than 20;
C) titanium oxide colloid that step b is obtained is warming up to 80-90 ℃, adds organic multicomponent acid brute force then and stirs, to regulate the faintly acid of pH value to 5.5-6.5; Described organic multicomponent acid including but not limited in citric acid, oxalic acid, acetate and the ethanedioic acid one or more;
D) for several times, be neutral, obtain white filter cake to the filter liquor pH value with the pure water washing and filtering; And with resulting white filter cake vacuum drying, the oven dry back adds industrial adhesion agent in the white loose powder that obtains, add terpinol behind the mixing, and the ball milling mixing obtains faint yellow titanium oxide colloid; Described industrial adhesion agent is an ethyl cellulose, the mass ratio 1 of described ethyl cellulose and titanium oxide: 1-5: 1;
E) the faint yellow titanium oxide colloid that steps d is obtained, the lower ethanol of boiling point is removed in decompression distillation, thereby obtains the titanium oxide coating material of steady concentration;
Second kind of preparation method:
A) tetrabutyl titanate or isopropyl titanate are joined in the ethanolic solution, be mixed with the tetrabutyl titanate of homogeneous transparent or the ethanolic solution of isopropyl titanate through stirring; Wherein the volume ratio of tetrabutyl titanate or isopropyl titanate and ethanol is 1: 2-1: 3;
B) tetrabutyl titanate of the homogeneous transparent that step a is prepared or the ethanolic solution of isopropyl titanate splash in a large amount of pure water, and brute force stirs the reaction that is hydrolyzed simultaneously, forms white anatase phase oxidation titanium colloid; Wherein the volume ratio of pure water and tetrabutyl titanate or titanium isopropoxide solution is greater than 20;
C) titanium oxide colloid that step b is obtained is warming up to 80-90 ℃, directly adopt a large amount of organic solvents to carry out washing and filtering to remove organic substance residues material wherein, the organic solvent that is adopted is a kind of solvent or several mixed solvent in methyl alcohol, ethanol, acetone and the benzene, and the volume ratio of positive fourth fat of employed organic solvent and metatitanic acid or isopropyl titanate is 20: 1-30: 1;
D) the white filter cake vacuum drying behind the washing and filtering adds ethyl cellulose after crushed after the oven dry, and the ethyl cellulose of adding and the mass ratio of titanium oxide are 1: 1-5: 1, and mix the back and add terpinol, obtain faint yellow titanium oxide colloid after grinding mixing again;
E) the faint yellow titanium oxide colloid that steps d is obtained, the lower ethanol of boiling point is removed in decompression distillation, thereby obtains the high viscosity titanium oxide coating material of specific concentrations.
3, require coating of titanium dioxide preparation methods in 2 described a kind of DSSC, it is characterized in that titanium oxide colloid is warming up to that temperature retention time is 20-24h under the 80-90 ℃ of condition.
4, by coating of titanium dioxide preparation methods in the described a kind of DSSC of claim 2, the temperature of the vacuum drying of white filter cake is 60-70 ℃ after it is characterized in that washing, filtering.
5, coating of titanium dioxide preparation methods in the described a kind of DSSC of claim 2 is characterized in that ethyl cellulose is to add with the ethanolic solution form of ethyl cellulose.
6, coating of titanium dioxide preparation methods in each described a kind of DSSC among the claim 1-4 is characterized in that prepared TiO
2The quality percentage composition of titanium oxide is 10%-20% in the coating material, TiO
2Crystallite dimension be 5nm-30nm.
7, by coating of titanium dioxide preparation methods in the described a kind of DSSC of claim 6, it is characterized in that principal crystalline phase is the anatase phase in the described coating material.
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| CN102280271B (en) * | 2010-11-29 | 2012-10-03 | 香港理工大学 | Preparation method of special silk-screen printing slurry for dye-sensitized solar cell |
| CN103035410B (en) * | 2011-10-08 | 2018-02-06 | 中国科学院上海硅酸盐研究所 | Dye sensitized optoelectronic converting device and its manufacture method, and metal oxide paste |
| CN102903527A (en) * | 2012-09-28 | 2013-01-30 | 彩虹集团公司 | Preparation method of dye-sensitized solar cell photo-anode paste |
| CN103021568A (en) * | 2012-12-10 | 2013-04-03 | 彩虹集团公司 | Preparation method of dye-sensitized solar cell slurry |
| CN109626410A (en) * | 2019-01-09 | 2019-04-16 | 无锡威孚环保催化剂有限公司 | A kind of preparation method of the adjustable neodymia colloidal sol of partial size |
| CN113462189B (en) * | 2021-06-25 | 2023-04-25 | 杭州映山花颜料化工有限公司 | Preparation method of azo pigment |
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