KR101978022B1 - Electrolyte composition for dye-sensitized solar cell and dye-sensitized solar cell comprising said electrolyte composition - Google Patents
Electrolyte composition for dye-sensitized solar cell and dye-sensitized solar cell comprising said electrolyte composition Download PDFInfo
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- KR101978022B1 KR101978022B1 KR1020160150823A KR20160150823A KR101978022B1 KR 101978022 B1 KR101978022 B1 KR 101978022B1 KR 1020160150823 A KR1020160150823 A KR 1020160150823A KR 20160150823 A KR20160150823 A KR 20160150823A KR 101978022 B1 KR101978022 B1 KR 101978022B1
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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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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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
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2072—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells comprising two or more photoelectrodes sensible to different parts of the solar spectrum, e.g. tandem 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
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention relates to an electrolyte composition for a dye-sensitized solar cell and a dye-sensitized solar cell comprising the electrolyte composition, and more particularly to a dye-sensitized solar cell comprising a window capable of transmitting sunlight; An optical electrode formed on one side of the window and including a transparent conductive electrode and a porous film on which the dye is adsorbed; And a counter electrode spaced apart from the photoelectrode, the electrolyte composition comprising 5-methylthio-1,3,4-thiadiazole-2-thiol ( 5-Methylthio-1,3,4-thiadiazole-2-thiol (MTD) and 5-methylthio-1,3,4-thiadiazole disulfide cation (MTD) 2 2+ ), and a dye-sensitized solar cell comprising the electrolyte composition. The present invention relates to a dye-sensitized solar cell comprising a dye-sensitized solar cell and a dye- A novel electrolytic composition solving the problem of a polysulfide-based electrolyte used in a sensitive solar cell and a dye-sensitized solar cell using the electrolytic composition can be provided to increase the light efficiency of the dye-sensitized solar cell.
Description
The present invention relates to an electrolyte composition for a dye-sensitized solar cell and a dye-sensitized solar cell comprising the electrolyte composition, and more particularly to a dye-sensitized solar cell comprising a window made of a material capable of transmitting sunlight; An optical electrode formed on one side of the window and including a transparent conductive electrode and a porous film on which the dye is adsorbed; And a counter electrode spaced apart from the photoelectrode, wherein the electrolytic composition comprises a 5-methylthio-1,3,4-thiadiazole- Methylthio-1,3,4-thiadiazole-2-thiol (MTD) and 5-methylthio-1,3,4-thiadiazole disulfide cations (5-Methylthio-1,3 , 4-thiadiazole disulfide cation (MTD) 2 2+ ), and a dye-sensitized solar cell comprising the electrolyte composition.
[Chemical Formula 1]
(2)
The dye-sensitized photovoltaic cell is represented by a photovoltaic solar cell disclosed by Gratzel et al., Switzerland in 1991. The dye-sensitized photovoltaic cell generally includes a photosensitive dye that absorbs visible light, a wide band gap energy , A counter electrode that is catalyzed, and an electrolyte filled therebetween. The dye-sensitized solar cell is advantageous in that its production cost is lower than that of a conventional silicon solar cell or a compound semiconductor solar cell, its efficiency is higher than that of an organic solar cell, and it is also environmentally friendly and transparent.
Recently, researches for increasing the light efficiency of a dye-sensitized solar cell have been concentrated. In particular, in the case of dyes, since light absorption occurs only in a specific wavelength band, a substance that absorbs light of a wavelength band not absorbed by the dye and converts the light into a light of a wavelength range capable of being absorbed by the dye, A method of mixing the electrolyte with the electrolyte to increase the light efficiency is used. These materials use solar energy with wavelengths that are not directly absorbed into the dye through fluorescence resonance energy transfer (FRET) or surface plasmon resonance (SPR) phenomena.
For example, Korean Patent Laid-Open No. 10-2012-40666 discloses a dye-sensitized solar cell comprising a photoelectrode (cathode), a counter electrode (anode), and an electrolyte between the electrodes, Wherein the photoelectrode comprises a semiconductor oxide thin film sequentially adsorbed through a chemical bond between a dye and a fluorescent material. However, in the dye-sensitized solar cells disclosed in the above-mentioned document, the efficiency is enhanced by the FRET effect, so that the effect can be expressed only when the dye and the fluorescent material are present near the Forster radius (about 1 nm or less). Therefore, the TiO 2- There is a structural limitation that the materials should be all in the adsorption structure, and the manufacturing process for manufacturing the same is also inevitably complicated. The present applicant also has recently disclosed a method of manufacturing a solar cell including a window made of a material capable of transmitting sunlight, a photo electrode including a nano-metal oxide formed on one side of the window and having a photo-sensitive dye adsorbed thereon and a counter electrode facing away from the photo electrode And an electrolyte filled between the photoelectrode and the counter electrode, wherein the electrolyte composition absorbs light in a short wavelength range in which the absorbance of the photo-sensitive dye is 60% or less, A dye-sensitized solar cell comprising an energy transfer material capable of emitting light energy in a wavelength range in which the absorbance of the dye is at least 60%, and a dye-sensitized solar cell comprising the electrolyte composition, (Korean Patent No. 1429759). The inventor's patent described above can be evaluated as a remarkably improved solar cell luminous efficacy improvement method because it can increase the light efficiency even by a simple method of adding the energy transfer material to the electrolyte without directly adsorbing the energy transfer material to the electrode. The present inventors have also found that the present invention provides a method of manufacturing a solar cell comprising a window capable of transmitting sunlight, a photoelectrode including a nano-metal oxide formed on one side of the window and adsorbing a photosensitive dye, and a counter electrode spaced apart from the photo- And a liquid-phase electrolytic composition filled between the photoelectrode and the counter electrode, wherein the electrolytic composition comprises iodine and nickel nanoparticles, wherein the dye-sensitized solar cell comprises iodine and nickel nanoparticles. (Patent Application No. 2016-4949). The invention of the present inventor, which is related to an electrolytic composition, utilizes the conversion of light of a wavelength band which could not be absorbed in conventional dyes into light of a wavelength range where dyes can utilize due to fluorescence resonance energy transfer phenomenon or surface plasmon resonance phenomenon Thereby enhancing the light efficiency of the entire solar cell.
Recently, organic dyes, inorganic dyes and hybrid dyes have been studied to replace dyes of ruthenium series in dye-sensitized solar cells. Among them, a quantum dot dye made of an inorganic semiconductor nanoparticle has a high extinction coefficient compared to a ruthenium-based dye, and can be applied to a flexible solar cell in the future, Unlike organic dyes, a single material has the property of absorbing wavelengths over the band gap in all regions, and has a low bandgap through quantum confinement with a size below the Bohr radius. The bandgap of a bulk material having a large thickness can be easily controlled. Also, excitons generated due to a high dielectric constant can be easily separated into electrons and holes, and it is possible to generate multiple exciton generation (MEG) in which one photon generates a large number of excitons , It is possible to apply a low-cost process because a solution process is possible. In general, quantum dot solar cells use a polysulfide type electrolyte. When the light is received, the quantum dots are corroded by the electrolyte, and the current value is rapidly decreased. It also has the disadvantage that the electrolyte absorbs the quantum dot absorption region.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel electrolytic composition for solving the problem of a polysulfide-based electrolyte applied to a dye-sensitized solar cell to which a quantum dot has been applied and a dye-sensitized solar cell to which the electrolytic composition is applied will be.
According to an aspect of the present invention, there is provided a solar cell comprising: a window made of a material capable of transmitting sunlight; An optical electrode formed on one side of the window and including a transparent conductive electrode and a porous film on which the dye is adsorbed; And a counter electrode spaced apart from the photoelectrode, wherein the electrolytic composition comprises a 5-methylthio-1,3,4-thiadiazole- Methylthio-1,3,4-thiadiazole-2-thiol (MTD) and 5-methylthio-1,3,4-thiadiazole disulfide cations (5-Methylthio-1,3 , 4-thiadiazole disulfide cation, (MTD) 2 2+ ). The present invention also provides an electrolyte composition for a dye-sensitized solar cell.
[Chemical Formula 1]
(2)
The present invention also provides a method of manufacturing a semiconductor device, wherein the porous film comprises at least one of Sn, Sn, Nb, (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Zn) oxide, magnesium (Mg) oxide, cadmium oxide, magnesium zinc (MgZn) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, gallium ) Oxide, zinc tin oxide (ZnSnO), titanium oxide (TiO2) and zinc indium tin (ZIS) oxide, nickel (Ni) oxide, rhodium (Rh) oxide, ruthenium (Ru) oxide, iridium (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide, titanium (Ti) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, lanthanum (La) oxide, vanadium Denominator (Mo) oxide, niobium (Nb) Characterized in that it is made of at least one metal oxide selected from the group consisting of aluminum oxide, aluminum oxide, yttrium oxide, scandium oxide, samarium oxide and strontium titanium oxide. An electrolytic composition for a sensitive solar cell is provided.
Further, the present invention relates to a dye-sensitized solar cell, Or porphyrine dyes, squarine dyes, materials having Q-bands between 500 and 600 nm, or ruthenium-based dyes of at least one selected from the group consisting of N719, N3, Ru505 and Z907 The present invention provides an electrolytic composition for a dye-sensitized solar cell.
The quantum dots may be CdS, CdSe, ZnS, PbS, PbTe, SnS, SnSe, SnTe, Sb2S3, AlN, AlP, AlAs, GaN, GaP, GaAs, InS, InP, InAs, InSb, Si, and Ge. The present invention provides an electrolytic composition for a dye-sensitized solar cell.
The present invention also provides an electrolyte composition for a dye-sensitized solar cell, wherein the bandgap of the quantum dot is in a range of 1.55 eV to 3.1 eV.
The present invention also relates to a window made of a material capable of transmitting sunlight; A photoelectrode formed on one side of the window and including a transparent conductive electrode and a porous film on which the dye is adsorbed; A counter electrode spaced apart from the photoelectrode; And 5-Methylthio-1,3,4-thiadiazole-2-thiol (hereinafter referred to as " 5-methylthio- , MTD) and a redox pair consisting of 5-methylthio-1,3,4-thiadiazole disulfide cation (MTD) 2 2+ of formula ( 2 ) The present invention provides a dye-sensitized solar cell comprising an electrolytic composition containing
[Chemical Formula 1]
(2)
The present invention also provides a method of manufacturing a semiconductor device, wherein the porous film comprises at least one of Sn, Sn, Nb, (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Zn) oxide, magnesium (Mg) oxide, cadmium oxide, magnesium zinc (MgZn) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, gallium ) Oxide, zinc tin oxide (ZnSnO), titanium oxide (TiO2) and zinc indium tin (ZIS) oxide, nickel (Ni) oxide, rhodium (Rh) oxide, ruthenium (Ru) oxide, iridium (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide, titanium (Ti) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, lanthanum (La) oxide, vanadium Denominator (Mo) oxide, niobium (Nb) Characterized in that it is made of at least one metal oxide selected from the group consisting of aluminum oxide, aluminum oxide, yttrium oxide, scandium oxide, samarium oxide and strontium titanium oxide. A photovoltaic cell is provided.
Further, the present invention relates to a dye-sensitized solar cell, Or porphyrine dyes, squarine dyes, materials having Q-bands between 500 and 600 nm, or ruthenium-based dyes of at least one selected from the group consisting of N719, N3, Ru505 and Z907 The present invention provides a dye-sensitized solar cell characterized by being a dye.
The quantum dots may be CdS, CdSe, ZnS, PbS, PbTe, SnS, SnSe, SnTe, Sb2S3, AlN, AlP, AlAs, GaN, GaP, GaAs, InS, InP, InAs, InSb, Si, and Ge. The present invention provides a dye-sensitized solar cell comprising at least one selected from the group consisting of InSb, Si, and Ge.
The present invention also provides a dye-sensitized solar cell characterized in that the bandgap of the quantum dot is in the range of 1.55 eV to 3.1 eV.
Further, the present invention is a method for manufacturing a transparent conductive electrode, wherein the transparent conductive electrode comprises an FTO (F-doped SnO 2 : SnO 2 : F), ITO, metal having an average thickness of 1 to 1,000 nm, metal nitride, metal oxide, The present invention provides a dye-sensitized solar cell characterized by being a conductive film.
Further, the present invention is characterized in that the metal nitride is a nitride of Group IVB metal, a nitride of Group VB metal, a nitride of Group VIB, aluminum nitride, Wherein the dye-sensitized solar cell is at least one selected from the group consisting of a dye-sensitized solar cell and a dye-sensitized solar cell.
The present invention also provides a method of manufacturing a semiconductor device, wherein the metal oxide is selected from the group consisting of Sn oxide, antimony (Sb), niobium (Nb), fluorine doped tin (Sn) oxide, indium (In) oxide, tin- (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Sn) Doped zinc (Zn) oxide, magnesium (Mg) oxide, cadmium oxide, magnesium zinc oxide, indium zinc oxide, copper aluminum oxide, silver oxide, Zinc oxide (ZNSO), titanium oxide (TiO2), zinc indium tin (ZIS) oxide, nickel (Ni) oxide, rhodium (Rh) oxide, ruthenium (Ru) oxide, iridium There is provided a dye-sensitized solar cell characterized in that the dye-sensitized solar cell is one type selected from the group consisting of copper (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide and titanium (Ti) oxide.
The present invention also provides a dye-sensitized solar cell, wherein the carbon compound is at least one selected from the group consisting of activated carbon, graphite, carbon nanotube, carbon black and graphene.
The present invention also provides a method for producing a conductive polymer, wherein the conductive polymer is at least one selected from the group consisting of PEDOT (poly (3,4-ethylenedioxythiophene) -PSS (poly (styrenesulfonate)), polyaniline-CSA, pentacene, polyacetylene, Hexylthiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy-4- (0 -dispersed red) At least one member selected from the group consisting of polypyridazines, polyisothianaphthalenes, polyphenylene sulfides, polyvinylpyridines, polythiophenes, polyfluorenes, polypyridines, polypyrroles, polysulfuronitrides, and copolymers thereof The present invention provides a dye-sensitized solar cell.
The present invention also provides a method of fabricating a semiconductor device, wherein the counter electrode comprises at least one selected from the group consisting of Pt, activated carbon, graphite, carbon nanotube, carbon black, p-type semiconductor, PEDOT (poly (3,4-ethylenedioxythiophene) ) -PSS (poly (styrenesulfonate)), polyaniline-CSA, pentacene, polyacetylene, P3HT (poly (3-hexylthiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, Polyphenylenevinylene, 4- (0-Dispersed Red 1) -2,5-phenylene-vinylene), polyindole, polycarbazole, polypyridazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, A dye-sensitized solar cell comprising a substrate and a film made of a material selected from the group consisting of polypyrrole, polypyridine, polypyrrole, polysulfuronitrile, derivatives thereof, and copolymers thereof, Lt; / RTI >
The present invention provides a novel electrolytic composition solving the problem of a polysulfide-based electrolyte applied to a dye-sensitized solar cell to which a quantum dot has been applied, and a dye-sensitized solar cell to which the electrolytic composition is applied, .
1 is a schematic diagram illustrating a structure of a dye-sensitized solar cell according to the present invention and a process of converting light energy into electrical energy occurring therein
FIG. 2 is a graph comparing the absorption of light of a conventional iodine-based electrolyte, a sulfur-based electrolyte and an electrolyte for a dye-sensitized solar cell according to the present invention
3 is a graph showing the relationship between the electrolyte
4 is a graph showing the relationship between the redox state of the electrolyte of the present invention and the sulfur-
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the drawings attached hereto.
It will be understood by those skilled in the art that the following embodiments are merely illustrative of the present invention and that various changes may be made without departing from the spirit and scope of the present invention. It can be deformed. Wherever possible, the same or similar parts are denoted using the same reference numerals in the drawings.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Means that a particular feature, region, integer, step, operation, element and / or component is specified and that the presence or absence of other features, regions, integers, steps, operations, elements, and / It does not exclude addition.
The term " nano, " as used herein, refers to a nanoscale ranging from 1 to 1,000 nm, and may optionally include microunits. In addition, the term " nanoparticles " described in the specification includes all types of particles having nanoscale. In the present specification, the term 'dyes' refers to all of light-sensitive materials in sunlight in a photoreactive solar cell such as a dye, which is a conventional organic compound in the conventional sense, and sometimes an inorganic quantum dot. Dye-sensitized solar cells' also use conventional 'dyes' as photosensitizers, solar cells using' Qdots' alone as photosensitizers, 'dye' and 'quantum dots' as photosensitizers Are used in the sense of collectively or collectively.
FIG. 1 is a schematic diagram for explaining the structure of a dye-sensitized solar cell according to the present invention and the conversion process of light energy into electrical energy occurring therein. The structure of the dye-sensitized solar cell to which the electrolytic composition for a dye-sensitized solar cell of the present invention is applied, as shown in FIG. 1, will be well known to those skilled in the art. No further detailed description of the structure of the battery or the battery cell will be given.
Meanwhile, in the present invention, the photoelectrode may be formed by a conventional method, and may include a transparent conductive electrode and a porous film on which the dye is adsorbed. In the present invention, the photoelectrode may be formed by a conventional method, and may include a transparent conductive electrode and a quantum dot adsorption porous film.
The transparent conductive electrode (TCO: transparent conducting oxide) is FTO (F-doped SnO 2: SnO 2: F), ITO, an average thickness of 1 to 1000nm is a metal electrode, metal nitrides, metal oxides, carbon compounds, or conductive polymer, And the like. Examples of the metal nitride include, but are not limited to, a group consisting of a nitride of Group IVB metal element, a nitride of Group VB metal element, a nitride of Group VIB element, aluminum nitride, gallium nitride, indium nitride, silicon nitride, germanium nitride, More than species can be selected. The metal oxide may be nanoparticles of 10 to 100 nm and the metal oxide nanoparticles may be selected from the group consisting of tin (Sn) oxide, antimony (Sb), niobium (Nb) or fluorine doped tin (Sn) ) Oxide, tin-doped indium oxide, zinc oxide, aluminum, boron, gallium, hydrogen, indium, yttrium, Ti), silicon (Si) or tin (Sn) doped zinc oxide, magnesium oxide, cadmium oxide, magnesium zinc oxide, indium zinc oxide, (Cu) oxide, silver (Ag) oxide, gallium (Ga) oxide, zinc tin oxide (ZnSnO), titanium oxide (TiO2) and zinc indium tin (ZIS) oxide, nickel (Ni) oxide, rhodium (Ru) oxide, iridium (Ir) oxide, copper (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide, titanium (Ti) oxide, zirconium (Zr) oxide, strontium (La) oxide, (V) oxide, molybdenum (Mo) oxide, niobium (Nb) oxide, aluminum (Al) oxide, yttrium oxide, scandium oxide, samarium oxide, strontium titanium ) Oxide, and titanium oxide is preferably used. The carbon compound may be selected from the group consisting of activated carbon, graphite, carbon nanotube, carbon black, graphene, and mixtures thereof. The conductive polymer may be selected from the group consisting of PEDOT (poly (3,4-ethylenedioxythiophene) -PSS (poly (styrene sulfonate)), polyaniline-CSA, pentacene, polyacetylene, P3HT Polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy-4- (0 -dispersed 1) -2,5-phenylene-vinylene), polyindole, polycarbazole, , Polyisothianaphthalene, polyphenylene sulfide, polyvinyl pyridine, polythiophene, polyfluorene, polypyridine, polypyrrole, polysulfuron nitride, and copolymers thereof. .
The porous film means a metal oxide. The nanoparticle film is formed on the transparent conductive electrode using TiO 2 or the like. At this time, the thickness of the porous film formed on the photo electrode is not particularly limited, but may be preferably 1 to 40 탆. The porous film may be formed by a conventional method using a paste containing metal oxide nanoparticles, a binder and a solvent, and a photosensitive dye, for example, a metal oxide nanoparticle paste containing metal oxide nanoparticles, a binder and a solvent on a transparent conductive electrode And then heat-treated at a temperature of 450 to 500 ° C for 1 to 2 hours. Thereafter, the step of adsorbing the dye and / or the quantum dots on the surface of the porous film can be performed to manufacture the photoelectrode. The porous film is not particularly limited and may be a known metal oxide such as tin oxide, antimony (Sb), niobium (Nb) or fluorine doped tin (Sn) oxide, indium (In) (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Sn) doped zinc oxide, magnesium oxide, cadmium oxide, magnesium zinc oxide, indium zinc oxide, copper aluminum oxide, silver (Ag) oxide, gallium (Ga) oxide, zinc tin oxide (ZnSnO), titanium oxide (TiO2) and zinc indium tin (ZIS) oxide, nickel oxide, rhodium oxide, ruthenium oxide (Ir) oxide, copper (Cu) oxide, cobalt (Co) oxide, tungsten (W) oxide, titanium (Ti) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, lanthanum Vanadium (V ) Oxide, a molybdenum (Mo) oxide, a niobium (Nb) oxide, an aluminum (Al) oxide, an yttrium (Y) oxide, a scandium (Sc) oxide, a samarium (Sm) oxide and a strontium titanium And at least one metal oxide nanoparticle selected from the group consisting of metal oxide nanoparticles.
The photosensitive material is not particularly limited, but may be a quantum dot. It is preferably a porpyrine dye, a squarine dye or a ruthenium dye having Q bands between wavelengths of 500 to 600 nm which is a visible light region. In particular, since the ruthenium-based dye has a MLCT (metal to ligand charge transfer) band, it is more preferable as an example of a photosensitive dye because the UV wavelength has a high absorbance at between about 530 and 610 nm. The ruthenium-based dye is preferably at least one selected from the group consisting of N719, N3, Ru505 and Z907. In addition, the quantum dots include at least one of CdS, CdSe, ZnS, PbS, PbSe, PbTe, SnS, SnSe, SnTe, Sb2S3, Sb2Se3, AlN, AlP, AlAs, GaN, GaP, GaAs, GaSb, InN, InP, InAs, Ge. Of these, quantum dots having a band gap of 1.55 eV to 3.1 eV and capable of absorbing visible light are preferable. For example, metal chalcogenide series include CdS, CdSe , CdTe, PbS, PbSe, and a complex thereof.
A transparent conductive electrode (TCO) may be formed on the conductive transparent substrate, for example, SnO 2 : F or ITO. However, , And can form ordinary conductive films well known in the art. Also, the conductive electrode may be at least one selected from the group consisting of FTO (F-doped SnO 2 : SnO 2 : F), ITO or metal electrode having an average thickness of 1 to 1000 nm, metal nitride, metal oxide, carbon compound, and conductive polymer A conductive film may be coated.
The electrolytic composition for a dye-sensitized solar cell of the present invention comprises a redox pair of 5-Methylthio-1,3,4-thiadiazole-2-thiol (MTD) and (MTD) 2 2+ . In the case of (MTD) 2 2+ , it can be prepared by adding an oxidizing agent to the MTD solution. The oxidizing agent is not particularly limited, and nitrosonium tetrafluoroborate (BF 4 NO) is used in the embodiment of the present invention. The redox pair may be used as an electrolyte by dissolving in a nonvolatile organic solvent at the time of production. The organic solvent is not particularly limited, and an organic solvent having a high boiling point, which shows sufficient solubility to the redox pair, such as dimethylsulfoxide, acetonitrile, 3-methoxypropionitrile, ethylene carbonate, propylene Carbonate, polyethylene glycol, polypropylene glycol, tetrahydrofuran and the like, room temperature molten salts including imidazolium, pyrrolidinium, and the like, and mixtures thereof.
The counter electrode may also be a counter electrode of a known dye-sensitized solar cell. In an embodiment of the present invention, a nanoparticle metal film using Pt or the like is used to form a counter electrode. Examples of the nanoparticle metal forming the counter electrode include platinum (Pt), activated carbon, graphite, carbon nanotube, carbon black, p-type semiconductor, PEDOT (poly (3,4- ) -PSS (poly (styrenesulfonate)), polyaniline-CSA, pentacene, polyacetylene, P3HT (poly (3-hexylthiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, Polyphenylenevinylene), poly (vinylidene fluoride), poly (vinylidene fluoride), poly (vinylidene fluoride), poly At least one member selected from the group consisting of thiophene, polyfluorene, polypyridine, polypyrrole, polysulfuronitrile, derivatives thereof, and copolymers thereof.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are provided for illustrative purposes only, and the scope of the present invention is not limited thereto.
[Example 1]
(Preparation of MTD / (MTD) 2 2+ electrolyte)
1 M MTD, 0.05 M nitrosonium tetrafluoroborate (BF 4 NO), 0.1 M lithium perchlorate (LiClO 4 ) and 1.2 M 4-tert-butylpyridine (tBP) dissolved in dimethylsulfoxide / acetonitrile (1:10 v / v) To prepare an electrolyte.
(Fabrication of photoelectrode)
A glass substrate (Philkington Company, material: FTO, thickness: 2.2 cm, 8? / Sq) was prepared as the substrate for the photoelectrode. Subsequently, a metal oxide nanoparticle paste containing 18.5% by weight of titanium oxide nanoparticles (average particle diameter: 20 nm), 0.05% by weight of a binder polymer (ethyl cellulose), and a residual solvent (Terpineol) After using the doctor blade method, the substrate was heat-treated at 500 DEG C for 30 minutes to form a porous film (thickness: 4.5 mu m) containing metal oxide nanoparticles. Subsequently, a metal oxide nanoparticle paste containing 18.5% by weight of titanium oxide nanoparticles (average particle diameter: 400 nm), 0.05% by weight of a binder polymer (ethyl cellulose), and a residual solvent (Terpineol) After using the doctor blade method, the substrate was heat-treated at 500 DEG C for 30 minutes to form a porous film (thickness: 3 mu m) containing metal oxide nanoparticles.
Next, the substrate was subjected to a successive ionic layer absorption reaction (SILAR) technique to adsorb the photosensitive quantum dots to the CdS / ZnS quantum dot dye to prepare a photoelectrode.
(Preparation of counter electrode)
A transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared as a substrate for a counter electrode. The transparent conductive electrode of the substrate was prepared by dissolving 0.05
[Experimental Example 1]
The energy conversion efficiency of the dye-sensitized solar cell using each of the electrolytes prepared in Example 1 was measured in the following manner. The results are shown in Table 1 below.
(1) Energy conversion efficiency (%)
: The energy conversion efficiency was measured using a solar simulator (Polaronix K201, McScience, AM1.5 filter, and power meter (Polaronix K101 / LAB20, McScience, Korea) of 1.5 Am 100 mW / cm2.
CdS QD
When MTD / (MTD) 2 2+ electrolyte of the present invention is compared with Polysulfide-based electrolyte using the same counter electrode using CdS QD, the current and voltage values are very high and FF is high, Good things can be found. In the case of the MTD / (MTD) 2 2+ electrolyte of the present invention, it can be seen that the difference between the current and the voltage is large depending on the counter electrode, and it is found that the optimum condition of the counter electrode is required. This means that the condition of the counter electrode that has been used previously must be changed as the electrolyte is changed. As shown in FIG. 4, in the case of the MTD / (MTD) 2 2+ electrolyte, the oxidation reduction level of the electrolyte is lower than that of the conventional sulfur-based electrolyte and has a similar redox level to that of the existing iodine-based electrolyte. have.
The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art will be able to modify the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the scope of the present invention as long as they are obvious to those skilled in the art.
Claims (16)
The electrolytic composition comprises 5-methylthio-1,3,4-thiadiazole-2-thiol (MTD) represented by the following formula (1) A redox pair consisting of 5-methylthio-1,3,4-thiadiazole disulfide cation (5-Methylthio-1,3,4-thiadiazole disulfide cation, (MTD) 2 2+ ) Electrolytic composition for sensitive solar cell.
[Chemical Formula 1]
(2)
The porous film may include at least one selected from the group consisting of Sn oxide, antimony (Sb), niobium (Nb) or fluorine doped Sn oxide, indium oxide, tin- (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Mg) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, gallium (Ga) oxide, zinc tin oxide, magnesium oxide, cadmium oxide, magnesium zinc A metal oxide such as an oxide (ZnSnO), a titanium oxide (TiO2), a zinc indium tin (ZIS) oxide, a nickel oxide, a rhodium oxide, a ruthenium oxide, an iridium oxide, A cobalt oxide, a tungsten oxide, a titanium oxide, a zirconium oxide, a strontium oxide, a lanthanum oxide, a vanadium oxide, a molybdenum oxide, , Niobium (Nb) oxide, aluminum (Al Characterized in that it is made of at least one metal oxide selected from the group consisting of oxides, yttrium (Y) oxides, scandium (Sc) oxides, samarium (Sm) oxides and strontium titanium (SrTi) oxides. Composition.
The dye may be a quantum dot; Or porphyrine dyes, squarine dyes, materials having Q-bands between 500 and 600 nm, or ruthenium-based dyes of at least one selected from the group consisting of N719, N3, Ru505 and Z907 Wherein the dye-sensitized solar cell is a dye-sensitized solar cell.
The quantum dots include at least one of CdS, CdSe, ZnS, PbS, PbSe, PbTe, SnS, SnSe, SnTe, Sb2S3, Sb2Se3, AlN, AlP, AlAs, GaN, GaP, GaAs, GaSb, InN, InP, InAs, And at least one member selected from the group consisting of an alkali metal salt and a metal salt.
Wherein the quantum dot has a band gap in a range of 1.55 eV to 3.1 eV.
A photoelectrode formed on one side of the window and including a transparent conductive electrode and a porous film on which the dye is adsorbed;
A counter electrode spaced apart from the photoelectrode;
And 5-Methylthio-1,3,4-thiadiazole-2-thiol (hereinafter referred to as " 5-methylthio- , MTD) and a redox pair consisting of 5-methylthio-1,3,4-thiadiazole disulfide cation (MTD) 2 2+ of formula ( 2 ) A dye-sensitized solar cell comprising an electrolytic composition comprising:
[Chemical Formula 1]
(2)
The porous film may include at least one selected from the group consisting of Sn oxide, antimony (Sb), niobium (Nb) or fluorine doped Sn oxide, indium oxide, tin- (Al), boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Mg) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, gallium (Ga) oxide, zinc tin oxide, magnesium oxide, cadmium oxide, magnesium zinc A metal oxide such as an oxide (ZnSnO), a titanium oxide (TiO2), a zinc indium tin (ZIS) oxide, a nickel oxide, a rhodium oxide, a ruthenium oxide, an iridium oxide, A cobalt oxide, a tungsten oxide, a titanium oxide, a zirconium oxide, a strontium oxide, a lanthanum oxide, a vanadium oxide, a molybdenum oxide, , Niobium (Nb) oxide, aluminum (Al Wherein the metal oxide is at least one metal oxide selected from the group consisting of oxides, yttrium (Y) oxides, scandium (Sc) oxides, samarium (Sm) oxides and strontium titanium (SrTi) oxides.
The dye may be a quantum dot; Or porphyrine dyes, squarine dyes, materials having Q-bands between 500 and 600 nm, or ruthenium-based dyes of at least one selected from the group consisting of N719, N3, Ru505 and Z907 Wherein the dye-sensitized solar cell is a dye.
The quantum dots include at least one of CdS, CdSe, ZnS, PbS, PbSe, PbTe, SnS, SnSe, SnTe, Sb2S3, Sb2Se3, AlN, AlP, AlAs, GaN, GaP, GaAs, GaSb, InN, InP, InAs, Wherein the dye-sensitized solar cell is at least one selected from the group consisting of a dye-sensitized solar cell and a dye-sensitized solar cell.
Wherein the quantum dot has a band gap of 1.55 eV to 3.1 eV.
The counter electrode may be formed of one selected from the group consisting of Pt, activated carbon, graphite, carbon nanotube, carbon black, p-type semiconductor, PEDOT (poly (3,4-ethylenedioxythiophene) (Poly (3-hexylthiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy- Dispersion Red 1) -2,5-phenylene-vinylene), polyindole, polycarbazole, polypyridazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene, polyfluorene , Polypyridine, polypyrrole, polysulfuronitrile, derivatives thereof, and copolymers thereof. The dye-sensitized solar cell according to claim 1, wherein the film is formed of a material selected from the group consisting of polypyridine, polypyrrole, polysulfone nitride, derivatives thereof and copolymers thereof.
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