KR20130120846A - High efficiency electrolyte for dye-sensitized solarcell - Google Patents
High efficiency electrolyte for dye-sensitized solarcell Download PDFInfo
- Publication number
- KR20130120846A KR20130120846A KR1020120044035A KR20120044035A KR20130120846A KR 20130120846 A KR20130120846 A KR 20130120846A KR 1020120044035 A KR1020120044035 A KR 1020120044035A KR 20120044035 A KR20120044035 A KR 20120044035A KR 20130120846 A KR20130120846 A KR 20130120846A
- Authority
- KR
- South Korea
- Prior art keywords
- dye
- electrolyte
- sensitized solar
- solar cell
- iodide
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 51
- 239000006096 absorbing agent Substances 0.000 claims abstract description 22
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- 238000000034 method Methods 0.000 claims description 14
- -1 metal complex salt Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
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Images
Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S30/00—Structural details of PV modules other than those related to light conversion
- H02S30/10—Frame structures
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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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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
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Abstract
Description
The present invention relates to a dye-sensitized solar cell, and more particularly, to a highly efficient dye-sensitized solar cell that can increase the efficiency of the cell by activating the reaction in the electrolyte by causing vibration of ions and molecules in the electrolyte. An electrolyte and a dye-sensitized solar cell comprising the same.
Recently, a variety of researches are being conducted to replace existing fossil fuels in order to solve the energy problems faced. Extensive research is underway to utilize natural energy sources such as wind, nuclear, and solar power to replace petroleum resources that will be depleted within decades. Among these solar cells, unlike other energy sources, the resources are infinite and environmentally friendly. So, since the development of Se solar cells in 1983, steady research has been continued, and silicon solar cells are in the spotlight recently.
However, since such a silicon solar cell is extremely expensive to manufacture, it is difficult to put it into practical use, and it is difficult to improve the battery efficiency. In order to overcome such problems, development of a dye-sensitized solar cell having a remarkably low manufacturing cost has been actively studied.
Dye-sensitized solar cells, developed in 1991 by Gratzel et al., Switzerland, are photosensitive dye molecules capable of absorbing visible light to produce electron-hole pairs, and nanocrystals that deliver the resulting electrons. A photoelectrochemical solar cell using an oxide semiconductor electrode made of oxidized titanium oxide particles, also called a dye-sensitized solar cell or a wet solar cell. Such a solar cell has a feature of having a photoelectric conversion efficiency that is simple in manufacturing process, low in manufacturing cost, and practically usable as compared with a silicon type solar cell, and many studies have been conducted on this.
In general, the dye-sensitized solar cell comprises a semiconductor electrode, a counter electrode, a liquid electrolyte. The semiconductor electrode is a porous nano oxide layer on a transparent substrate and a transparent conductive oxide layer formed on the transparent substrate, for example, a porous nano oxide layer on a conductive transparent substrate including fluorine-doped tin oxide (FTO) or indium tin oxide (ITO). Has a structure in which dye is adsorbed. The counter electrode has a structure in which a platinum catalyst layer is formed on a conductive transparent substrate including a transparent substrate and a transparent conductive oxide layer formed on the transparent substrate to promote a reduction reaction of the electrolyte in the liquid electrolyte. In the liquid electrolyte, a solution in which an electrolyte is dissolved is generally used. The liquid electrolyte is disposed between the semiconductor electrode and the counter electrode to be in contact with both electrodes electrochemically. Here, a sidewall made of a thermoplastic polymer resin or the like is formed between the semiconductor electrode and the counter electrode to form a space in which the electrolyte is injected between the semiconductor electrode and the counter electrode.
Such dye-sensitized solar cells are attracting attention because they are cheaper to manufacture than conventional silicon solar cells and can be applied to glass windows or glass greenhouses due to transparent electrodes, but they are practically applied due to their low photoelectric conversion efficiency. There is a limit.
Accordingly, researches for improving the photoelectric conversion efficiency of dye-sensitized solar cells have been conducted in various aspects, and the present invention intends to improve the photoelectric conversion efficiency of dye-sensitized solar cells by improving the performance of the electrolyte.
An object of the present invention is a dye-sensitized electrolyte including a dye-sensitized solar cell which can improve the photoelectric conversion efficiency by causing a vibratory movement of ions and molecules in the electrolyte to make the electrical reaction in the electrolyte more active. To provide a solar cell.
The present invention to achieve the above object, an organic solvent; Oxidation-reduction derivatives; And it provides a dye-sensitized solar cell electrolyte comprising a light absorber.
As the organic solvent, those selected from the group consisting of acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, tetrahydrofuran, 3-methoxypropionnitrile and gamma-butyrolactone may be used. Can be. However, the present invention is not limited thereto.
Examples of the oxidation-reduction derivative include iodine; And one or more mixtures selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salts, imidazolium salts and pyridinium salts. However, the present invention is not limited thereto.
The dye-sensitized solar cell electrolyte may further include an additive selected from the group consisting of t-butylpyridine and 2-dimethylamino pyridine.
The dye-sensitized solar cell electrolyte may further include a supporting electrolyte selected from the group consisting of imidazolium-based iodide, pyridinium-based iodide, and pyrrolinium-based iodide.
The content of the light absorbing agent is preferably 0.05 to 5.0 parts by weight based on 100 parts by weight of the electrolyte. However, the present invention is not limited thereto.
The present invention also provides a dye-sensitized solar cell comprising the electrolyte.
According to the electrolyte for a dye-sensitized solar cell of the present invention, by introducing a light absorbing agent, the light incident on the cell causes vibrational movement of ions and molecules in the electrolyte so that battery reaction occurs more actively, thereby improving photoelectric conversion efficiency. Can be.
1 is a view schematically showing the structure of a dye-sensitized solar cell according to an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing a dye-sensitized solar cell according to an embodiment of the present invention.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.
1 is a view schematically showing the structure of a dye-sensitized solar cell according to an embodiment of the present invention. Referring to the dye-sensitized solar cell of the present invention with reference to Figure 1 as follows.
The dye-sensitized solar cell of the present invention includes a semiconductor electrode 100, a
The semiconductor electrode 100 includes a
The
The transparent conductive layer 120 may be formed of indium tin oxide (FTO) or indium tin oxide (ITO) doped with fluorine.
The
The dye may be adsorbed using a solution containing a ruthenium complex or an organic dye. As dyes, ruthenium complexes, including ruthenium complexes, which can absorb visible light, and any dyes capable of improving long-wavelength absorption in visible light to improve efficiency and efficient electron emission can be used. to be. Specifically, xanthine-based dyes such as rhodamine B, rosebengal, eosin, erythrosin and the like; Cyanine-based dyes such as quinocyanine and cryptocyanine; Basic dyes such as phenosafranin, cabrioblue, thiocin and methylene blue; Porphyrin compounds such as chlorophyll, zinc porphyrin and magnesium porphyrin; Other azo dyes; Phthalocyanine compounds; Anthraquinone dyes; Or polycyclic quinone dye etc. can be used individually or in mixture of 2 or more types.
Meanwhile, the
The
The
A light absorber is a material that absorbs light of a certain wavelength to cause rotation, vibration, and translational movement of atoms and molecules, and emits energy and heat as the motion of these materials occurs.
When the light absorbing agent is introduced into the electrolyte, light corresponding to the vibration level energy difference is incident to vibrate motion of the ions and molecules in the electrolyte, so that the movement of the ions and molecules is accelerated. Ions are transferred.
As the light absorbing agent, the compound of Formula 1 may be, for example, PMMA resin-containing compound, Benzophenone compound, Benzotriazole compound, Salicylate compound, Cyanoacrylate compound, Oxanilide compound, Hindered amine (HALS) compound, Metal complex salt light Purification can be used. They do not react with existing liquid electrolyte components and can be prepared by simple mixing without a separate process.
[Formula 1]
As the organic solvent, for example, acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, 3-methoxypropionnitrile, gamma-butyrolactone, and the like may be used.
In addition, the redox derivatives are, for example, iodine; And at least one selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salts, imidazolium salts and pyridinium salts.
In addition, additives such as t-butylpyridine or 2-dimethylamino pyridine may be further added to the dye-sensitized solar cell of the present invention.
In addition, the dye-sensitized solar cell of the present invention may further comprise a supporting electrolyte in addition to the organic solvent, redox derivatives and additives, the supporting electrolyte is imidazolium-based iodide, pyridinium-based iodide or pyrroli Nium-based iodide and the like can be used. Specific examples thereof include 1-ethyl-3-methylimidazolium iodide, 1-methyl-3-methylimidazolium iodide, and 1-methyl-3-methylimidazolium iodide. ) Or 1-butylpyridinium iodide (1-Butylpyridinium iodide) and the like.
The content of the light absorbing agent in the
2 is a flowchart illustrating a method of manufacturing a dye-sensitized solar cell according to an embodiment of the present invention. Referring to Figure 2 describes the manufacturing method of the dye-sensitized solar cell of the present invention.
Method for manufacturing a dye-sensitized solar cell according to the present invention comprises the steps of manufacturing the semiconductor electrode 100, manufacturing the
The manufacturing of the semiconductor electrode 100 may include preparing a
Specifically, first, after preparing the
The manufacturing of the
Specifically, first, after preparing the
Next, the semiconductor electrode 100 and the
Next, after preparing a liquid electrolyte by mixing an organic solvent, a redox derivative, a light absorbing agent, and the like, the prepared liquid electrolyte is injected and sealed between the semiconductor electrode 100 and the
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
Example
< Example 1>
(1) Fabrication of Semiconductor Electrodes
After cutting the FTO substrate having a sheet resistance of 8Ω using a diamond glass cutter, three-stage ultrasonic cleaning was performed using deionized water, alcohol, and acetone. Then, a colloidal TiO 2 nano paste having a particle size of 20 nm was coated on the FTO substrate with an area of 8 mm * 87 mm and a thickness of 80 μm using a screen printer, and then heated in an electric furnace for 1 hour from room temperature to 550 ° C. Sintering was carried out for 30 minutes. Since anhydrous alcohol and ruthenium-based dye N719 (Taiwan, EVERLIGHT) was prepared at a concentration of 0.3 mM, the sintered TiO 2 semiconductor electrode was immersed at 40 ° C. for 18 hours to allow the dye to adsorb.
(2) Preparation of counter electrode
After cutting the FTO substrate having a sheet resistance of 8Ω using a diamond glass cutter, an electrolyte injection hole was formed, and then three-stage ultrasonic cleaning was performed using deionized water, alcohol, and acetone. Thereafter, Pt paste (Dysol) was applied using a screen printer, and the counter electrode was manufactured by sintering for 30 minutes in an electric furnace through a temperature raising step of 1 hour from room temperature to 400 ° C.
(3) Preparation of Electrolyte
3-Methoxypropionitrile, 0.1M LiI, 0.05MI 2 , 0.3-0.7M 1-Ethyl-3-methylimidazoliumiodide, 0.3-0.5Mt-Butylpyridine, and a light absorber were mixed and stirred for 30 minutes to prepare an electrolyte solution (in the liquid electrolyte. The concentrations of LiI, I 2 , 1-Ethyl-3-methylimidazolium iodide and t-Butylpyridine are concentrations based on the total liquid electrolyte). The light absorber was added at 0.5% by weight based on 100 parts by weight of the liquid electrolyte.
(4) Manufacture of Dye-Sensitized Solar Cell
Surlyn (Dupont) having a thickness of about 60 μm was formed on the junction surface of the semiconductor electrode and the counter electrode, and then the electrode was bonded by sintering at 100 to 140 ° C. for 1 to 4 minutes. Next, after the electrolyte was injected between the semiconductor electrode and the counter electrode through the electrolyte injection hole to seal the injection hole using a PI tape to manufacture a dye-sensitized solar cell.
≪ Comparative Example 1 &
A dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that no light absorbing agent was added at the time of preparing the electrolyte.
≪ Test Example 1 >
After the aging for 48 hours for the dye-sensitized solar cell prepared in Example 1 and Comparative Example 1, the cell was exposed to the outside to perform an outdoor test. Long-term stability of the electrolyte was evaluated by the outdoor test, and as a result of checking the leakage of the electrolyte, it was confirmed that it operated without leakage of the electrolyte for 360 hours.
≪ Test Example 2 &
The light conversion efficiency of the dye-sensitized solar cells prepared in Example 1 and Comparative Example 1 was evaluated by the following method.
Photovoltaic properties were observed by measuring the photovoltage and photocurrent, and the light conversion efficiency (ηe) was obtained using the current density (Jsc), the voltage (Voc), and the filling factor (ff) obtained through the photovoltaic characteristics. Equation 1 below was used to calculate the light conversion efficiency. In this case, a xenon lamp (Oriel) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was corrected using a standard solar cell.
[Equation 1]
ηe = (Voc × Jsc × ff) / (Pine)
Where (Pine) represents 100 mW / cm 2 (1 sun)
The values measured through the above process are shown in Table 1 below.
Through the results of Table 1, the dye-sensitized solar cell using the liquid electrolyte of Example 1 to which the light absorber was added when the liquid electrolyte was prepared compared to the dye-sensitized solar cell of Comparative Example 1 without the light absorber ( Jsc), the voltage (Voc), and the fill factor (ff) is very excellent, it can be confirmed by the high light conversion efficiency that the light absorber to actively perform the battery reaction in the electrolyte.
Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the accompanying drawings. Naturally, it belongs to the scope of the invention.
100: semiconductor electrode 110: transparent substrate
120: transparent conductive film 130: photoelectrode
200: counter electrode 210: transparent substrate
220: transparent conductive film 230: catalyst layer
300: electrolyte 400: sidewalls
Claims (8)
Oxidation-reduction derivatives; And
An electrolyte for dye-sensitized solar cells, comprising a light absorber.
The light absorbing agent is a compound represented by Formula 1, PMMA resin-containing compound, Benzophenone-based compound, Benzotriazole-based compound, Salicylate-based compound, Cyanoacrylate-based compound, Oxanilide-based compound, Hindered amine (HALS) -based compound, metal complex salt-based light stabilizer Dye-sensitized solar cell electrolyte, comprising a.
[Chemical Formula 1]
The organic solvent is selected from the group consisting of acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, tetrahydrofuran, 3-methoxypropionnitrile and gamma-butyrolactone. Dye-sensitized solar cell electrolyte.
The oxidation-reduction derivatives include iodine; And at least one mixture selected from the group consisting of lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salts, imidazolium salts and pyridinium salts. .
A dye-sensitized solar cell electrolyte further comprising an additive selected from the group consisting of t-butylpyridine and 2-dimethylamino pyridine.
An electrolyte for dye-sensitized solar cells, further comprising a supporting electrolyte selected from the group consisting of imidazolium-based iodide, pyridinium-based iodide, and pyrrolinium-based iodide.
The content of the light absorbing agent is a dye-sensitized solar cell electrolyte, characterized in that 0.05 to 5.0 parts by weight relative to 100 parts by weight of the electrolyte.
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| CN111149056A (en) * | 2017-10-11 | 2020-05-12 | 东丽株式会社 | Photosensitive conductive paste and film for forming conductive pattern |
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| CN111149056A (en) * | 2017-10-11 | 2020-05-12 | 东丽株式会社 | Photosensitive conductive paste and film for forming conductive pattern |
| CN111149056B (en) * | 2017-10-11 | 2023-07-25 | 东丽株式会社 | Photosensitive conductive paste and conductive pattern forming film |
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