CN100517772C - An electrode of quantum dot sensitization solar battery and the corresponding preparation method - Google Patents
An electrode of quantum dot sensitization solar battery and the corresponding preparation method Download PDFInfo
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- CN100517772C CN100517772C CNB2007103077378A CN200710307737A CN100517772C CN 100517772 C CN100517772 C CN 100517772C CN B2007103077378 A CNB2007103077378 A CN B2007103077378A CN 200710307737 A CN200710307737 A CN 200710307737A CN 100517772 C CN100517772 C CN 100517772C
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Abstract
The invention relates to an electrode of a quantum dot-sensitized solar cell and the preparation method, octadecene, tributyl phosphate and selenium powder are mixed to prepare a selenium precursor; oleic acid, octadecene and cadmium oxide power are mixed to prepare a cadmium precursor; the nano titanium dioxide powder is dispersed in an octadecene solution of titanium dioxide which is prepared in the octadecene, the octadecene solution of the titanium dioxide is washed and dried in the mixed solution of cadmium precursor and selenium precursor so as to obtain a quantum dot-sensitized titanium dioxide nanocrystal; the quantum dot-sensitized titanium dioxide powder and a non-ionic surfactant are mixed and ground to prepare a paste, the paste is evenly coated on a transparent conductive substrate to form a thin film, and finally sintering is carried out. As the quantum dots are directly in-situ synthesized at the surface of titanium dioxide, the quantum dots are closely combined with the titanium dioxide particles, thus the invention is beneficial to the improvement of the stability of the cell and the photoelectric conversion efficiency; furthermore, the quantum dots which are generated under an oily system have very high crystallinity and luminous efficiency, thus the invention is beneficial to the further improvement of the efficiency of the solar cell.
Description
Technical field
The invention belongs to DSSC material field, be specifically related to a kind of quantum dot sensitized electrode of solar battery and preparation method thereof.
Background technology
Along with global energy crisis is serious day by day, the urgent hope of people can be found a kind of clean energy resource of sustainable development.Solar energy receives the concern of countries in the world day by day as a kind of inexhaustible natural energy source.DSSC is compared with the traditional silicon solar cell, and is with low cost, makes simply, becomes the focus of various countries' scholar's research.In the manufacturing process of DSSC, one of its committed step is exactly the wide bandgap semiconductor film to be carried out sensitization handle.
The dyestuff that tradition is used for sensitization mostly is organic dyestuff or metal-organic complex, but discontinuous, the less stable of this class dyestuff absorption spectrum, has limited the photoelectric properties of prepared solar cell greatly.With the luminescent semiconductor nanocrystal crystalline substance, promptly general said quantum dot as photosensitizer, has then overcome above-mentioned shortcoming.Absorbing 1 photon with general dyestuff, can only to produce 1 electronics at most different, and quantum dot can produce 3 electronics by 1 solar photon, can be electric energy with the solar energy converting 65% or more in theory, almost is the twice that has solar battery efficiency now.
The method of present quantum dot sensitized titanium dioxide photoelectrode mainly contains two kinds: 1. the wide bandgap semiconductor film is immersed in the quantum dot colloidal sol, make quantum dot attached on the film by suction-operated; 2. alternately the wide bandgap semiconductor film is immersed in two kinds of salting liquids, generate quantum dot at film surface.Quantum dot is by the suction-operated combination among first kind of preparation method, and the size of quantum dot is regulated by the concentration of salting liquid in the less stable of battery, second kind of preparation method, and the quantum dot crystallinity of generation is relatively poor, and electricity conversion is lower.Given this, provide the DSSC that a kind of quantum dot combines with semiconductor electrode film closely, photoelectric conversion efficiency is high to necessitate.
Summary of the invention
The purpose of this invention is to provide a kind of quantum dot sensitized electrode of solar battery that can improve the photoelectricity conversion performance of DSSC.
Another object of the present invention is to provide a kind of preparation quantum dot sensitization solar battery electrode and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is:
1) the quantum dot sensitized titanium dioxide nanocrystalline of preparation CdSe
The preparation of selenium presoma: by 1: 0.8～1: 2 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 0.8mmol: 1ml～1.1mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 20～1: 4 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 10ml～1mmol: 30ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: 5ml～1g: the 10ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 200-310 ℃ by 1: 1～1: 2 volume ratio in room temperature and obtain mixed liquor, be that 3: 2～6: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 200-600 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
Nonionic surface active agent of the present invention is acetylacetone,2,4-pentanedione or polyethylene glycol.
According to the quantum dot sensitized electrode of solar battery that preparation method of the present invention obtains, comprise a transparent conduction base sheet and be grown in the nanometer crystal film that has luminescent quantum dot on this transparent conduction base sheet.
The titanium dioxide nanocrystalline that the CdSe that adopts preparation method of the present invention to obtain is quantum dot sensitized, because quantum dot is synthetic at the titanium dioxide surface direct in-situ, therefore quantum dot combines with TiO 2 particles closely, help improving the stability and the electricity conversion of battery, and the quantum dot that under the oiliness system, generates, have very high degree of crystallinity and luminous efficiency, help further improving solar battery efficiency.
Description of drawings
Fig. 1 is the solar battery apparatus figure that adopts electrode of the present invention.
Embodiment
The preparation of selenium presoma: by 1: 1.5 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 0.8mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 4 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 10ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: the 5ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 200 ℃ by 1: 2 volume ratio in room temperature and obtain mixed liquor, be that 1.5: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent acetylacetone,2,4-pentanedione and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 600 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
Embodiment 2,1) the quantum dot sensitized titanium dioxide nanocrystalline of preparation CdSe
The preparation of selenium presoma: by 1: 1.0 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 1.0mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 12 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 17ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: the 8ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 260 ℃ by 1: 1.5 volume ratio in room temperature and obtain mixed liquor, be that 3: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent polyethylene glycol and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 300 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
The preparation of selenium presoma: by 1: 0.8 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 0.9mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 15 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 24ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: the 10ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 290 ℃ by 1: 1 volume ratio in room temperature and obtain mixed liquor, be that 4.5: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent acetylacetone,2,4-pentanedione and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 500 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
The preparation of selenium presoma: by 1: 2 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 1.1mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 20 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 30ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: the 6ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 310 ℃ by 1: 2 volume ratio in room temperature and obtain mixed liquor, be that 6: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent polyethylene glycol and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 200 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
Referring to Fig. 1, the quantum dot sensitized electrode of solar battery of making by preparation method of the present invention: comprise a transparent conduction base sheet 1 and be grown in the nanometer crystal film that has luminescent quantum dot 2 on this transparent conduction base sheet 1, battery electrode of the present invention is placed the electrolyte solution 3 of iodine/lithium iodide, electro-conductive glass light anode 4 is connected and can uses with transparent conduction base sheet 1.
Claims (3)
1, the preparation method of quantum dot sensitized electrode of solar battery is characterized in that:
1) the quantum dot sensitized titanium dioxide nanocrystalline of preparation CdSe
The preparation of selenium presoma: by 1: 0.8～1: 2 volume ratio octadecylene and tributyl phosphate being mixed and to obtain mixed solution, is that the ratio of 0.8mmol: 1ml～1.1mmol: 1ml joins selenium powder and makes the selenium presoma in the mixed liquor in selenium powder and mixed solution then;
The preparation of cadmium presoma: by 1: 20～1: 4 volume ratio oleic acid and octadecylene being mixed and to obtain mixed solution, is that the ratio of 1mmol: 10ml～1mmol: 30ml joins cadmium oxide and is heated to dissolving fully in the mixed solution makes the cadmium presoma under nitrogen protection in cadmium oxide powder and mixed solution then;
In 1g: 5ml～1g: the 10ml ratio is dispersed in nano-titanium dioxide powder the octadecylene solution of making titanium dioxide in the octadecylene, the octadecylene solution of titanium dioxide is joined in the cadmium presoma and is heated to 200-310 ℃ by 1: 1～1: 2 volume ratio in room temperature and obtain mixed liquor, be that 3: 2～6: 1 mol ratio joins the selenium presoma in the mixed liquor by selenium and cadmium again, reaction 1-600 is cooled to room temperature after second, can obtain the quantum dot sensitized titanium dioxide nanocrystalline of CdSe, it is stand-by to make powder after the washing drying;
2) the quantum dot sensitized titanium dioxide nanocrystalline film of preparation CdSe
The titanium dioxide powder that the CdSe of above-mentioned preparation is quantum dot sensitized, nonionic surface active agent and water are made slurry by 4: 1: 6 quality than mixed grinding, this slurry is uniformly coated on forms film on the transparent conduction base sheet, 200-600 ℃ of following sintering 15 minutes to 12 hours, can obtain the quantum dot sensitized titanium dioxide nanocrystalline film of CdSe.
2, the preparation method of quantum dot sensitized electrode of solar battery according to claim 1 is characterized in that: the nonionic surface active agent that is produced is acetylacetone,2,4-pentanedione or polyethylene glycol.
3, the electrode that obtains of the preparation method of quantum dot sensitized electrode of solar battery according to claim 1 is characterized in that: comprise a transparent conduction base sheet (1) and be grown in the nanometer crystal film that has luminescent quantum dot (2) on this transparent conduction base sheet (1).
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Families Citing this family (16)
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| CN101515506B (en) * | 2009-04-08 | 2011-01-05 | 哈尔滨工业大学 | Method for preparing Bi2S3 quantum dot sensitized TiO2 membrane electrodes |
| CN101719534B (en) * | 2009-11-13 | 2011-10-05 | 彩虹集团公司 | Preparing method of organic thin film solar cell |
| US20120031490A1 (en) * | 2010-08-03 | 2012-02-09 | Honeywell International Inc. | Quantum dot solar cells and methods for manufacturing such solar cells |
| CN102181934B (en) * | 2010-08-09 | 2013-08-21 | 苏州晶瑞化学有限公司 | Environment-friendly biological texture etch solution and application method thereof |
| CN102097214B (en) * | 2010-11-21 | 2012-07-04 | 沈阳工业大学 | Preparation method of zinc oxide-based solar cell electrode |
| CN102360962B (en) * | 2011-09-30 | 2013-08-28 | 中国科学院等离子体物理研究所 | Preparation method of quantum dot sensitized solar cell |
| CN103021668B (en) * | 2012-12-28 | 2016-02-10 | 清华大学 | A kind of semiconductor nano crystal sensitized solar battery and preparation method thereof |
| CN103887353A (en) * | 2014-03-20 | 2014-06-25 | 梅景华 | Coating for converting optical energy into electric energy and glass assembly |
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| US11127937B2 (en) * | 2015-11-25 | 2021-09-21 | Research & Business Foundation Sungkyunkwan University | Method of manufacturing carbon-coated electrode active material and electrode active material manufactured by the method |
| CN105489383B (en) * | 2015-12-28 | 2018-03-09 | 华侨大学 | A kind of preparation method of quantum dot sensitized solar battery light anode |
| CN107065289B (en) * | 2017-05-26 | 2020-06-09 | 海信视像科技股份有限公司 | Quantum dot color filter, preparation method, liquid crystal panel and liquid crystal display device |
| CN106990464B (en) * | 2017-05-26 | 2020-01-14 | 青岛海信电器股份有限公司 | Quantum dot color filter, preparation method, liquid crystal panel and liquid crystal display device |
| CN107742580B (en) * | 2017-09-15 | 2019-06-28 | 华南农业大学 | A method of quantum dot solar battery is prepared based on light absorption paint |
| CN107946079B (en) * | 2017-11-15 | 2020-03-10 | 青岛大学 | Preparation of flexible full-printing quantum dot sensitized solar cell |
| CN112195027B (en) * | 2020-09-21 | 2022-06-28 | 天津纳美纳米科技有限公司 | Luminescent microsphere and preparation method thereof |
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