CN102543476A - Graphene counter electrode for dye-sensitized solar cell and manufacturing method of graphene counter electrode - Google Patents
Graphene counter electrode for dye-sensitized solar cell and manufacturing method of graphene counter electrode Download PDFInfo
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- CN102543476A CN102543476A CN2012100432580A CN201210043258A CN102543476A CN 102543476 A CN102543476 A CN 102543476A CN 2012100432580 A CN2012100432580 A CN 2012100432580A CN 201210043258 A CN201210043258 A CN 201210043258A CN 102543476 A CN102543476 A CN 102543476A
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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
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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
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Abstract
The invention relates to a graphene counter electrode for a dye-sensitized solar cell, belonging to the technical field of solar cells. The graphene counter electrode comprises a transparent substrate, a graphene conducting layer and a graphene catalyst layer, wherein the graphene conducting layer is arranged on the surface of the transparent substrate, the graphene catalyst layer is arranged on the surface of the graphene conducting layer; the graphene catalyst layer is manufactured by coating slurry formed by mixing graphene (or graphene-doped) powder, hydroxyethylcellulose and a volatile organic solvent on the graphene conducting layer, and drying a mixture. According to the graphene counter electrode disclosed by the invention, graphene is taken as a conducting layer to replace a traditional conducting thin film, such as ITO (Indium Tin Oxide); graphene powder with very large specific surface area as a catalyst layer takes the place of traditional metal platinum particles and has better catalysis effect. The graphene counter electrode disclosed by the invention has the characteristics of large area, low cost and high efficiency, the manufacturing process of the graphene counter electrod is simple, and a flexible electrode is conveniently obtained, thus the invention is hopeful to prompt the application of the graphene in the solar field, in particular the aspect of flexible dye-sensitized solar cells.
Description
Technical field
The invention belongs to technical field of solar batteries, relate to DSSC, especially DSSC electrode structure and preparation method thereof.
Background technology
Energy problem is the hot issue that influences human survival and development always.Solar energy is a kind of cleaning, and efficient with never depleted new forms of energy can provide stable energy supply to the mankind.DSSC as one of third generation solar cell is with low cost with it, preparation is simple and be expected to drop into practical application.The DSSC structure is made up of three parts: light anode, electrolyte and to electrode, and its operation principle is following: (1) dye molecule is accepted behind the solar light irradiation by ground state transition to excitation state; (2) dye molecule that is in excitation state is injected into electronics in the conduction band of light anode (being generally semiconductor); (3) behind the conductive film of electrons spread to light anode, the external circuit of flowing through; (4) be in the electrolyte reducing/regenerating that the dyestuff of oxidation state is had reproducibility; (5) electrolyte that is in oxidation state is reduced after electrode is accepted electronics, thereby accomplishes a circulation.Catalytic performance to electrode directly has influence on the ability that the electrolyte that is in oxidation state is accepted electronics, thereby the quick magnificent Solar cell performance of dyestuff is exerted an influence.
Existing DSSC is to electrode, and normally deposition one deck has the metal platinum particles of catalytic performance on Conducting Glass, thereby shape is to electrode.But this but have following deadly defect to electrode structure: on the one hand, though metal platinum has excellent catalytic performance to electrode, the metal platinum price is extremely expensive; On the other hand, its conductive layer of existing electro-conductive glass mainly is tin oxide (ITO) material that indium mixes, and indium is very rare as a kind of strategic resource; Moreover the flexibility of ITO electro-conductive glass is very little, reaches at 4% o'clock at stress usually, and the conductivity of ITO conductive film can receive heavy damage.All of these factors taken together all big limitations the development of the quick magnificent solar cell of dyestuff to electrode, thereby hindered the application of the quick magnificent solar cell of dyestuff.
2004, the Graphene (Graphene) that professor Geim of Univ Manchester UK finds was a kind of carbonaceous membrane new material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape structure.Theoretical research is found: the conductivity of Graphene can be compared with copper mutually, simultaneously the graphene film of monolayer carbon atom reach 97.7%, four layer of carbon atom at the light transmittance of visible region the light transmittance of Graphene still about 90%.This makes Graphene can be widely used in the transparency electrode field.Simultaneously, discover that Graphene has very high specific area, makes it have higher catalytic efficiency.In recent years, adopting the chemical liquid phase reducing process is that the low-cost graphene powder that feedstock production goes out is applied to fields such as gas sensing, dye cell with the graphite powder, and its excellent performance has been reconfirmed the great potential of graphene powder at catalytic field.
Summary of the invention
The present invention provides a kind of used by dye sensitization solar battery Graphene to electrode and preparation method thereof.The present invention at first is transferred to the transparent substrates surface with Graphene; Deposit the Graphene Catalytic Layer that one deck is made up of graphene powder or doped graphene then again on the Graphene surface; Obtain a kind of the novel of DSSC that can be used for to electrode; This Graphene has large tracts of land, low cost and high-efficiency characteristics to electrode, and its preparation process is simple, and is convenient to obtain flexible electrode; Thereby be expected to promote Graphene in field of solar energy, especially the application of flexible dye-sensitized solar battery aspect.
Technical scheme of the present invention is following:
A kind of used by dye sensitization solar battery Graphene is to electrode, comprises transparent substrates, is positioned at the graphene conductive layer on transparent substrates surface and is positioned at the Graphene Catalytic Layer of graphene conductive laminar surface; Said graphene conductive layer obtains and is transferred to the transparent substrates surface by existing Graphene growing method; Said Graphene Catalytic Layer mix by graphene powder or doped graphene powder, hydroxyethylcellulose and volatile organic solvent that the gained slurry is coated on the graphene conductive layer and oven dry to remove volatile organic solvent resultant.
In the technique scheme: 1) said transparent substrates is rigid glass substrates or flexible plastic substrate; 2) said graphene powder is the graphene powder by the preparation of chemical liquid phase reducing process; 3) said doped graphene powder is a kind of or any kind doping gained of graphene powder in nitrogen, sulphur, boron element by the preparation of chemical liquid phase reducing process; 4) the mass mixing ratio example of said graphene powder or doped graphene powder and hydroxyethylcellulose is 10: 1.
A kind of used by dye sensitization solar battery Graphene may further comprise the steps the preparation method of electrode:
Step 1: will have the Graphene that graphene preparation method obtains now and be transferred to the transparent substrates surface, and obtain being positioned at the graphene conductive layer on transparent substrates surface;
Step 2: graphene powder, hydroxyethylcellulose and the volatile organic solvent of chemical liquid phase reducing process preparation mixed the gained slurry be coated on the graphene conductive layer and volatile organic solvent is removed in oven dry, or mix back gained doped graphene powder, hydroxyethylcellulose and volatile organic solvent of a kind of or any kind of graphene powder in nitrogen, sulphur, boron element of chemical liquid phase reducing process preparation mixed the gained slurry and be coated on the graphene conductive layer and dry and remove volatile organic solvent; Obtain being positioned at the Graphene Catalytic Layer of graphene conductive laminar surface.
Need to prove:
1, the graphene conductive layer is through the preparation of existing graphene preparation method and be transferred to the transparent substrates surface; For the electric conductivity that increases the graphene conductive layer can increase the transfer number (1～2 time) of Graphene as one sees fit, promptly suitably increase the thickness of graphene conductive layer.
2, the graphene powder of existing chemical liquid phase reducing process preparation; When being mixed with slurry with the hydroxyethylcellulose that plays the binding agent effect; At first hydroxyethylcellulose is dissolved in volatile organic solvent (playing peptizaiton), sneaks into graphene powder then, obtain the Graphene slurry after the grinding evenly.
When 3, graphene powder being mixed preparation doped graphene powder, institute's doping elements can be that a kind of or any kind in nitrogen, sulphur, the boron element is mixed, and doping ratio is not limit; Doping method can be to the graphene powder of chemical liquid phase reducing process preparation through with the corresponding Cement Composite Treated by Plasma of doped chemical, also can be to carry out hydrothermal treatment consists or calcination processing then through soaking with the corresponding chemical solution of doped chemical.
Used by dye sensitization solar battery Graphene provided by the invention is to electrode, and the employing Graphene to replace existing tin indium oxide conductive films such as (ITO), plays electric action as conductive layer; And the Catalytic Layer that is positioned at the graphene conductive laminar surface adopts the very big graphene powder of specific area, and to replace existing metal platinum particles, its catalytic effect is better, more helps the electrolyte reduction.Used by dye sensitization solar battery Graphene provided by the invention is to electrode; Have large tracts of land, low cost and high-efficiency characteristics; Its preparation process is simple; And be convenient to obtain flexible electrode, thereby be expected to promote Graphene, the especially application of flexible dye-sensitized solar battery aspect in field of solar energy.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to embodiment.
Embodiment 1, adopt Graphene through the preparation of chemical liquid phase reducing process as the Graphene of Graphene Catalytic Layer to electrode, its concrete steps are following:
On metal, prepare Graphene through chemical vapour deposition technique, through existing transfer techniques Graphene is transferred on the glass substrate, repetitive displacement twice makes to have three layer graphenes on the glass substrate as the graphene conductive layer.To drip small amount of ethanol through the graphene powder and the hydroxyethylcellulose mixed grinding of chemical liquid phase reducing process preparation, continue to grind the formation slurry.Graphene powder wherein, the mass mixing ratio example between hydroxyethylcellulose and the ethanol is: 30mg: 3mg: 2ml.The mode that adopt to apply is coated on slurry on the graphene conductive layer, obtains final Graphene in 1 hour to electrode 180 ℃ air ambient held then.
Test finds that this Graphene is 8 Ω to the contact resistance of electrode, utilizes this DSSC that assembling forms to electrode, and its open circuit voltage reaches 0.75V, and efficient reaches 5%.
Embodiment 2, adopt nitrogen-doped graphene as the Graphene of Graphene Catalytic Layer to electrode, its concrete steps are following:
On metal, prepare Graphene through chemical vapour deposition technique, through existing transfer techniques Graphene is transferred on the glass substrate, repetitive displacement once makes to have two layer graphenes on the glass substrate as the graphene conductive layer.To be scattered in the ammoniacal liquor through the graphene powder of chemical liquid phase reducing process preparation, under 100 ℃ thermal and hydric environment, handled 10 hours then, obtain the nitrogen-doped graphene powder.With nitrogen-doped graphene powder and hydroxyethylcellulose mixed grinding, drip small amount of ethanol, continue to grind the formation slurry.Nitrogen-doped graphene powder wherein, the mass mixing ratio example between hydroxyethylcellulose and the ethanol is: 30mg: 3mg: 2ml.The method that adopt to apply is coated on slurry on the graphene conductive layer, obtains final Graphene in 1 hour to electrode 180 ℃ air ambient held then.
Test finds that this Graphene is 5 Ω to the contact resistance of electrode, utilizes this DSSC that assembling forms to electrode, and its open circuit voltage reaches 0.76V, and efficient reaches 8%.
Embodiment 3, adopt the boron doped graphene as the Graphene of Graphene Catalytic Layer to electrode, its concrete steps are following:
On metal, prepare Graphene through chemical vapour deposition technique, through existing transfer techniques graphene film is transferred on the plastic, repetitive displacement once makes to have two layer graphenes on the plastic as the graphene conductive layer.To place in the quartz boat through the graphene powder of chemical liquid phase reducing process preparation, feed diborane 200Pa, 500 ℃ are incubated 5 hours down, obtain boron doped graphene powder.With boron doped graphene powder and hydroxyethylcellulose mixed grinding, drip small amount of ethanol, continue to grind the formation slurry.Boron doped graphene powder wherein, between hydroxyethylcellulose and the ethanol the mass mixing ratio example be: 30mg: 3mg: 2ml.The method that adopt to apply is coated on slurry on the graphene conductive layer, obtains final Graphene in 1 hour to electrode 180 ℃ air ambient held then.
Test finds that this Graphene is 4 Ω to the contact resistance of electrode, utilizes this DSSC that assembling forms to electrode, and its open circuit voltage reaches 0.75V, and efficient reaches 7%.
Claims (10)
1. a used by dye sensitization solar battery Graphene is to electrode, comprises transparent substrates, is positioned at the graphene conductive layer on transparent substrates surface and is positioned at the Graphene Catalytic Layer of graphene conductive laminar surface; Said graphene conductive layer obtains and is transferred to the transparent substrates surface by existing Graphene growing method; Said Graphene Catalytic Layer mix by graphene powder or doped graphene powder, hydroxyethylcellulose and volatile organic solvent that the gained slurry is coated on the graphene conductive layer and oven dry to remove volatile organic solvent resultant.
2. used by dye sensitization solar battery Graphene according to claim 1 is characterized in that to electrode said transparent substrates is rigid glass substrates or flexible plastic substrate.
3. used by dye sensitization solar battery Graphene according to claim 1 and 2 is characterized in that to electrode said graphene powder is the graphene powder by the preparation of chemical liquid phase reducing process; Said doped graphene powder is a kind of or any kind doping gained of graphene powder in nitrogen, sulphur, boron element by the preparation of chemical liquid phase reducing process.
According to claim 1 or 3 described used by dye sensitization solar battery Graphenes to electrode, it is characterized in that said volatile organic solvent is an ethanol.
5. used by dye sensitization solar battery Graphene according to claim 4 is characterized in that to electrode the mixed proportion of said graphene powder or doped graphene powder, hydroxyethylcellulose and ethanol is 30mg: 3mg: 2ml.
6. a used by dye sensitization solar battery Graphene may further comprise the steps the preparation method of electrode:
Step 1: will have the Graphene that graphene preparation method obtains now and be transferred to the transparent substrates surface, and obtain being positioned at the graphene conductive layer on transparent substrates surface;
Step 2: graphene powder, hydroxyethylcellulose and the volatile organic solvent of chemical liquid phase reducing process preparation mixed the gained slurry be coated on the graphene conductive layer and volatile organic solvent is removed in oven dry, or mix back gained doped graphene powder, hydroxyethylcellulose and volatile organic solvent of a kind of or any kind of graphene powder in nitrogen, sulphur, boron element of chemical liquid phase reducing process preparation mixed the gained slurry and be coated on the graphene conductive layer and dry and remove volatile organic solvent; Obtain being positioned at the Graphene Catalytic Layer of graphene conductive laminar surface.
7. used by dye sensitization solar battery Graphene according to claim 6 is characterized in that to the preparation method of electrode said transparent substrates is rigid glass substrates or flexible plastic substrate.
According to claim 6 or 7 described used by dye sensitization solar battery Graphenes to the preparation method of electrode, it is characterized in that said volatile organic solvent is an ethanol.
According to claim 6 or 7 described used by dye sensitization solar battery Graphenes to the preparation method of electrode, it is characterized in that the mixed proportion of said graphene powder or doped graphene powder, hydroxyethylcellulose and ethanol is 30mg: 3mg: 2ml.
10. used by dye sensitization solar battery Graphene according to claim 9 is characterized in that the preparation method of electrode, and drying condition described in the step 2 is 180 ℃ an air ambient held 1 hour.
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Cited By (8)
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| CN102903539A (en) * | 2012-10-24 | 2013-01-30 | 上海大学 | Preparation method of graphene thick-film electrode |
| CN104047060A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院上海微系统与信息技术研究所 | Sulfur doping method for graphene |
| TWI511356B (en) * | 2012-11-21 | 2015-12-01 | Ind Tech Res Inst | Graphene electrode, energy storage device employing the same, and method for fabricating the same |
| CN105140038A (en) * | 2015-09-16 | 2015-12-09 | 大连理工大学 | Selenium-doped graphene counter electrode and preparation method thereof |
| CN107068407A (en) * | 2017-01-03 | 2017-08-18 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN109727779A (en) * | 2018-12-12 | 2019-05-07 | 青岛科技大学 | A kind of doping type graphene quantum dot and compound complete graphene-based to electrode and its preparation method and application of modified graphene |
| CN112768249A (en) * | 2020-12-30 | 2021-05-07 | 山东力诺光伏高科技有限公司 | Green and environment-friendly graphene solar cell and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903539A (en) * | 2012-10-24 | 2013-01-30 | 上海大学 | Preparation method of graphene thick-film electrode |
| TWI511356B (en) * | 2012-11-21 | 2015-12-01 | Ind Tech Res Inst | Graphene electrode, energy storage device employing the same, and method for fabricating the same |
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| CN104047060A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院上海微系统与信息技术研究所 | Sulfur doping method for graphene |
| CN105140038A (en) * | 2015-09-16 | 2015-12-09 | 大连理工大学 | Selenium-doped graphene counter electrode and preparation method thereof |
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN107068407A (en) * | 2017-01-03 | 2017-08-18 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN109727779A (en) * | 2018-12-12 | 2019-05-07 | 青岛科技大学 | A kind of doping type graphene quantum dot and compound complete graphene-based to electrode and its preparation method and application of modified graphene |
| CN112768249A (en) * | 2020-12-30 | 2021-05-07 | 山东力诺光伏高科技有限公司 | Green and environment-friendly graphene solar cell and preparation method thereof |
| CN112768249B (en) * | 2020-12-30 | 2022-07-22 | 山东力诺光伏高科技有限公司 | Green and environment-friendly graphene solar cell and preparation method thereof |
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Application publication date: 20120704 |