CN101777430B - Preparation method for titanium dioxide membrane used as dye-sensitized solar cell photo-anode - Google Patents
Preparation method for titanium dioxide membrane used as dye-sensitized solar cell photo-anode Download PDFInfo
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- CN101777430B CN101777430B CN2010101242160A CN201010124216A CN101777430B CN 101777430 B CN101777430 B CN 101777430B CN 2010101242160 A CN2010101242160 A CN 2010101242160A CN 201010124216 A CN201010124216 A CN 201010124216A CN 101777430 B CN101777430 B CN 101777430B
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- titanium dioxide
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- organic carrier
- anode
- dye
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a preparation method for a titanium dioxide membrane used as a dye-sensitized solar cell photo-anode. The preparation method comprises the following steps that: A. ethyecellulose is mixed with terpinol and is agitated in water bath to obtain organic carriers; B. carbon nano tubes and P25 nanocrystalline are put into a mortar and are ground after the organic carriers are added, and organic carrier nano titanium dioxide slurry is obtained; and C. the obtained nano titanium dioxide slurry is printed on conducting glass through screen printing to form the titanium dioxide membrane, the conducting glass is sintered in a muffle furnace, the temperature of the muffle furnace is increased by the rate of 5 DEG C per minute, when the temperature reaches 500 DEG C, the temperature is kept constant for 15min and then is naturally decreased to obtain the required titanium dioxide membrane and the titanium dioxide membrane can be used as the dye-sensitized solar cell photo-anode. When the titanium dioxide membrane prepared through the method is used as the dye-sensitized solar cell photo-anode, the sunlight absorptivity of the photo-anode is improved, the transmission speed of electrons is improved, the photoelectric conversion efficiency is improved and the performance of the cell is improved.
Description
[technical field]
The present invention relates to the preparation method of a kind of solar cell, particularly a kind of titanium dioxide membrane used as dye-sensitized solar cell photo-anode.
[background technology]
Along with the exhaustion of global fossil energy and the aggravation of problem of environmental pollution, the utilization of solar energy resources has caused the concern in the world, and simultaneously, the research of solar cell also becomes worldwide research focus.In various solar cells, DSSC is simple with its manufacture craft, be convenient to large-scale production, with low cost etc., and advantage more and more receives extensive attention.
In DSSC, the performance of porous light anode is particularly important to the Effect on Performance of battery, and is therefore, also more and more about the research of photo-anode film for many years.For realizing absorbing dye as much as possible; Realize simultaneously contacting with the firm of conductive substrates; And realize effective transmission of oxidation-reduction pair transmission and the electrolyte of electronics from dyestuff excitation state to conductive substrates, thereby the technology of preparing of porous light anode is very crucial.
In the preparation process of titanium dioxide nanocrystalline membrane electrode, the size of titanium dioxide crystal, crystal formation constitute, the porosity of film etc. all affects the efficient of battery.The method for preparing at present titanium dioxide nano-crystal mainly contains: hydro thermal method, Sol-gel method etc., and wherein best with the hydro thermal method effect, document P.Wang; Etc.J.Phys.Chem.B, 107 (2003) 14336, reported the titania slurry hydrothermal preparing process; This method cost is higher; Energy conversion efficiency has only 7.2%, and therefore, its preparation technology remains further to be improved.
In view of above problem, be necessary in fact to improve, to overcome above-mentioned defective to above technology.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode, and its light anode is strong to the absorption of sunlight, and the transmission rate of electronics is high, and energy conversion efficiency is high.
For solving above technical problem, the invention provides a kind of preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode, may further comprise the steps:
(1) preparation of organic carrier
In 80 ℃ water-bath, be 1 according to mass ratio: (5-10) ethyl cellulose being dissolved in the terpinol, stirring 2h, is the organic carrier of 5.9-6.1 thereby form viscosity, for future use;
(2) preparation of titania slurry
According to mass ratio is 1: (5-9) get the nanocrystalline mortar of putting into of CNT and P25, wherein, the particle diameter of CNT is (20-100) nm; The nanocrystalline particle diameter of P25 is 25nm; Then, add the organic carrier that obtains in the first step, grind 1h; Thereby obtain the organic carrier nano titania slurry, wherein solid content is 18%-24%;
(3) preparation of titanium dioxide film
A) nano titania slurry that obtains in second step is printed onto the electro-conductive glass substrate, thereby in the electro-conductive glass substrate, forms the layer of titanium dioxide film; B) be passed to drier, dry 15min under 80 ℃; C) be passed to sintering in the Muffle furnace, Muffle furnace heats up with the speed of 5 ℃/min, insulation 15min when temperature reaches 450 ℃, insulation 15min when temperature reaches 500 ℃; D) natural cooling promptly obtains required titanium dioxide film, as dye-sensitized solar cell anode.
Compared with prior art; The preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode of the present invention has the following advantages at least: owing to adopt TiO2 slurry nanocrystalline and the mixed preparation of CNT organic carrier; Therefore, the prepared TiO2 film that comes out has bigger specific surface and electric conductivity preferably, has strengthened the absorption of light anode to sunlight; Improve the transmission and the energy conversion efficiency of electronics simultaneously, and then effectively improved the performance of battery.
[embodiment]
Embodiment one:
(1) preparation of organic carrier
The 15g ethyl cellulose is added in the 75g terpinol, at 80 ℃ stirred in water bath 2h, is the organic carrier of 6.1cp thereby form viscosity, for future use;
(2) preparation of titania slurry
The CNT of getting the 2.4g particle diameter and be 20nm and 21.6g particle diameter are to put into agate mortar after nanocrystalline mixing of commercial titanium dioxide (P25) of 25nm; Adding the viscosity that the 76g first step obtains again is the organic carrier of 6.1cp; Fully grind 1h, thereby form the organic carrier nano titania slurry, wherein; The nanocrystalline mass ratio of CNT and P25 is 1: 9, and solid content is 24%;
(3) preparation of titanium dioxide film
A) titania slurry that on clean conductive glass substrate, adopts silk-screen printing technique to obtain with second step of 250 purpose stainless steel pringtings, thus the layer of titanium dioxide film formed at the electro-conductive glass substrate surface;
B) with steps A) device that obtains is passed in the drying box, at 80 ℃ of dry 15min;
C) with step B) device that obtains is passed to and carries out sintering in the Muffle furnace, and wherein Muffle furnace is that 5 ℃/min heats up with speed, and successively at 450 ℃ of insulation 15min, 500 ℃ of insulation 15min;
D) last, with step C) the device natural cooling that obtains, promptly obtain required titanium dioxide film, as the light anode of DSSC.
Embodiment two:
(1) preparation of organic carrier
The 15g ethyl cellulose is added in the 105g terpinol, at 80 ℃ stirred in water bath 2h, is the organic carrier of 6.0cp thereby form viscosity, for future use.
(2) preparation of titania slurry
The CNT of getting the 3.0g particle diameter and be 100nm and 15.0g particle diameter are that the P25 of 25nm puts into agate mortar after nanocrystalline the mixing; And the viscosity that the adding 82g first step obtains is the organic carrier of 6.0cp; Fully grind 1h, form the organic carrier nano titania slurry, wherein; The nanocrystalline mass ratio of CNT and P25 is 1: 5, and solid content is 18%.
(3) preparation of titanium dioxide film
A) titania slurry that on clean conductive glass substrate, adopts silk-screen printing technique to obtain with second step of 250 purpose stainless steel pringtings, thus the layer of titanium dioxide film formed in the electro-conductive glass substrate;
B) with steps A) device that obtains is passed in the drying box, at 80 ℃ of dry 15min;
C) with step B) device that obtains is passed to and carries out sintering in the Muffle furnace, and Muffle furnace is that 5 ℃/min heats up with speed, and successively at 450 ℃ of insulation 15min, 500 ℃ of insulation 15min;
D) with step C) the device natural cooling that obtains, promptly obtain required titanium dioxide film, thickness 15 μ m are as the light anode of DSSC.
Embodiment three:
(1) preparation of organic carrier
The 10g ethyl cellulose is added in the 100g terpinol, at 80 ℃ stirred in water bath 2h, is the organic carrier of 5.9cp thereby form viscosity, for future use.
(2) preparation of titania slurry
The carbon nano-crystal of getting the 3.0g particle diameter and be 60nm and 18g particle diameter are that the P25 of 25nm puts into agate mortar after nanocrystalline the mixing; And the viscosity that the adding 79g first step obtains is the organic carrier of 5.9cp; Fully grind 1h, form the organic carrier nano titania slurry, wherein; The nanocrystalline mass ratio of CNT and P25 is 1: 6, and solid content is 21%.
(3) preparation of titanium dioxide film
A) titania slurry that on clean conductive glass substrate, adopts silk-screen printing technique to obtain with second step of 250 purpose stainless steel pringtings, thus the layer of titanium dioxide film formed in the electro-conductive glass substrate;
B) with steps A) device that obtains is passed in the drying box, at 80 ℃ of dry 15min;
C) with step B) device that obtains is passed to sintering in the Muffle furnace, and Muffle furnace is that 5 ℃/min heats up with speed, and successively at 450 ℃ of insulation 15min, 500 ℃ of insulation 15min;
D) with step C) the device natural cooling that obtains, promptly obtain required titanium dioxide film, thickness 20 μ m are as the light anode of DSSC.
To be assembled in the battery respectively according to titanium dioxide film and traditional P 25 nano titanium dioxide films that preparation method of the present invention prepares; Wherein, battery be platinum electrode to electrode, dyestuff is the N719 of 0.3mol/L; Redox electrolytes liquid is: in acetonitrile solvent, and 0.05mol/L I
2, 0.1mol/L LiI, 0.4mol/L TBP, and the solar simulator of employing Oriel, simulation AM1.5, exposure light power is 1000W/m
2, and test the I-V curve of above-mentioned two kinds of batteries with the Keithley data source, the result is as shown in the table:
| Label | Short circuit current J SC(mA/cm 2) | Open circuit voltage V OC(mV) | Fill factor, curve factor F.F | Photoelectric conversion rate η (%) | Solid content (%) | C/Ti |
| 1-(25nmTi) | 4.89 | 670 | 0.55 | 4.89 | 21 | 0 |
| 2-(20nmC/25nmTi) | 5.59 | 698 | 0.56 | 5.59 | 24 | 1∶10 |
| 3-(100nmC/25nmTi) | 5.56 | 670 | 0.57 | 5.56 | 18 | 1∶5 |
| 4-(60nmC/25nmTi) | 5.34 | 699 | 0.54 | 5.34 | 21 | 1∶7 |
In the last table; The 1st group of data are traditional with the photoelectric properties of P25 nano titanium dioxide film as the battery of battery light anode, and the 2nd, 3,4 group of data are respectively with the photoelectric properties of the resulting titanium dioxide film of embodiment 1,2,3 preparation methods as the battery of battery light anode.
By can finding out in the above table, the titanium dioxide film for preparing with preparation method of the present invention is as the light anode of battery, its battery short circuit electric current, open circuit voltage, and fill factor, curve factor all increases, and photoelectric conversion rate is the highest to have improved 14.3%, and effect is remarkable.
The above is merely one embodiment of the present invention; It or not whole or unique execution mode; The conversion of any equivalence that those of ordinary skills take technical scheme of the present invention through reading specification of the present invention is claim of the present invention and contains.
Claims (4)
1. the preparation method of a titanium dioxide membrane used as dye-sensitized solar cell photo-anode may further comprise the steps:
(1) preparation of organic carrier
In 80 ℃ water-bath, be 1 according to mass ratio: (5-10) ethyl cellulose being dissolved in the terpinol, stirring 2h, is the organic carrier of 5.9-6.1cp thereby form viscosity, for future use;
(2) preparation of titania slurry
According to mass ratio is 1: (5-9) get CNT and titanium dioxide nanocrystalline is put into mortar, wherein, the particle diameter of CNT is (20-100) nm; The particle diameter of titanium dioxide nanocrystalline is 25nm; Then, add the organic carrier that obtains in the first step, grind 1h; Thereby obtain the organic carrier nano titania slurry, wherein solid content is 18%-24%;
(3) preparation of titanium dioxide film
A) the organic carrier nano titania slurry that obtains in second step is printed onto the electro-conductive glass substrate, thereby in the electro-conductive glass substrate, forms the layer of titanium dioxide film; B) be passed to drier, dry 15min under 80 ℃; C) be passed to sintering in the Muffle furnace, Muffle furnace heats up with the speed of 5 ℃/min, insulation 15min when temperature reaches 450 ℃, insulation 15min when temperature reaches 500 ℃; D) natural cooling promptly obtains required titanium dioxide film, as dye-sensitized solar cell anode.
2. the preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) preparation of organic carrier
In 80 ℃ water-bath, the 15g ethyl cellulose is dissolved in the 75g terpinol, stir 2h, be the organic carrier of 6.1cp thereby form viscosity, for future use;
(2) preparation of titania slurry
Get and put into agate mortar after titanium dioxide nanocrystalline that CNT that the 2.4g particle diameter is 20nm and 21.6g particle diameter be 25nm mixes; Add the organic carrier that 76g obtained in (1) step; Grind 1h, thereby obtain the organic carrier nano titania slurry, wherein solid content is 24%;
(3) preparation of titanium dioxide film
A) with the organic carrier nano titania slurry that obtains in second step with 250 purpose stainless steel pringtings to the electro-conductive glass substrate, thereby in the electro-conductive glass substrate formation layer of titanium dioxide film; B) be passed to drier, dry 15min under 80 ℃; C) be passed to sintering in the Muffle furnace, Muffle furnace heats up with the speed of 5 ℃/min, insulation 15min when temperature reaches 450 ℃, insulation 15min when temperature reaches 500 ℃; D) natural cooling promptly obtains required titanium dioxide film, as dye-sensitized solar cell anode.
3. the preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) preparation of organic carrier
In 80 ℃ water-bath, the 15g ethyl cellulose is dissolved in the 105g terpinol, stir 2h, be the organic carrier of 6.0cp thereby form viscosity, for future use;
(2) preparation of titania slurry
Get and put into agate mortar after titanium dioxide nanocrystalline that CNT that the 3.0g particle diameter is 100nm and 15.0g particle diameter be 25nm mixes; Add the organic carrier that 82g obtained in (1) step; Grind 1h, thereby obtain the organic carrier nano titania slurry, wherein solid content is 18%;
(3) preparation of titanium dioxide film
A) with the organic carrier nano titania slurry that obtains in second step with 250 purpose stainless steel pringtings to the electro-conductive glass substrate, thereby in the electro-conductive glass substrate formation layer of titanium dioxide film; B) be passed to drier, dry 15min under 80 ℃; C) be passed to sintering in the Muffle furnace, Muffle furnace heats up with the speed of 5 ℃/min, insulation 15min when temperature reaches 450 ℃, insulation 15min when temperature reaches 500 ℃; D) natural cooling promptly obtains required titanium dioxide film, as dye-sensitized solar cell anode.
4. the preparation method of titanium dioxide membrane used as dye-sensitized solar cell photo-anode as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) preparation of organic carrier
In 80 ℃ water-bath, the 10g ethyl cellulose is dissolved in the 100g terpinol, stir 2h, be the organic carrier of 5.9cp thereby form viscosity, for future use;
(2) preparation of titania slurry
Get and put into agate mortar after titanium dioxide nanocrystalline that CNT that the 3.0g particle diameter is 60nm and 18g particle diameter be 25nm mixes; Add the organic carrier that 79g obtained in (1) step; Grind 1h, thereby obtain the organic carrier nano titania slurry, wherein solid content is 21%;
(3) preparation of titanium dioxide film
A) with the organic carrier nano titania slurry that obtains in second step with 250 purpose stainless steel pringtings to the electro-conductive glass substrate, thereby in the electro-conductive glass substrate formation layer of titanium dioxide film; B) be passed to drier, dry 15min under 80 ℃; C) be passed to sintering in the Muffle furnace, Muffle furnace heats up with the speed of 5 ℃/min, insulation 15min when temperature reaches 450 ℃, insulation 15min when temperature reaches 500 ℃; D) natural cooling promptly obtains required titanium dioxide film, as dye-sensitized solar cell anode.
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| CN103198924A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院化学研究所 | Photo-anode of dye-sensitized solar cell and preparation method thereof |
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| CN102122580B (en) * | 2010-12-21 | 2012-05-30 | 北京化工大学 | Method for preparing modified titanium dioxide nanotube dye-sensitized photoanode thin film |
| CN102103931B (en) * | 2011-01-13 | 2012-07-18 | 宁波大学 | Nitrogen-doped titanium dioxide light anode and preparation method and application thereof |
| CN102231304B (en) * | 2011-03-28 | 2013-01-16 | 彩虹集团公司 | Method for preparing nano TiO2 (titanium dioxide) pastes |
| CN103903859A (en) * | 2012-12-27 | 2014-07-02 | 中国科学院上海硅酸盐研究所 | Method for preparing photoanode of dye-sensitized solar cell through coating |
| CN109908883A (en) * | 2019-01-24 | 2019-06-21 | 华东师范大学 | Nano carbon-base metal oxide composite and preparation method with photoelectrocatalysis function |
| CN114477380B (en) * | 2021-12-29 | 2023-06-23 | 天津科技大学 | Preparation method of functionalized electrode and application of functionalized electrode in photoelectrocatalysis treatment of solubilized organic sewage |
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| US6706963B2 (en) * | 2002-01-25 | 2004-03-16 | Konarka Technologies, Inc. | Photovoltaic cell interconnection |
| CN101521114A (en) * | 2009-03-31 | 2009-09-02 | 彩虹集团公司 | Preparation method for laminated photo-anode film of dye-sensitized solar cell |
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| WO2003098731A1 (en) * | 2002-05-20 | 2003-11-27 | Hitachi Maxell, Ltd. | Photoelectric conversion device |
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| US6706963B2 (en) * | 2002-01-25 | 2004-03-16 | Konarka Technologies, Inc. | Photovoltaic cell interconnection |
| CN101521114A (en) * | 2009-03-31 | 2009-09-02 | 彩虹集团公司 | Preparation method for laminated photo-anode film of dye-sensitized solar cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103198924A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院化学研究所 | Photo-anode of dye-sensitized solar cell and preparation method thereof |
| CN103198924B (en) * | 2013-04-12 | 2015-12-23 | 中国科学院化学研究所 | Light anode of DSSC and preparation method thereof |
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