KR20130028953A - Dye-sensitized solar cells and manufacturing methods thereof - Google Patents

Abstract

PURPOSE: A dye-sensitized solar cell and a manufacturing method thereof are provided to improve the optical efficiency of a metal oxide fuel cell by blocking three-valent iodine ions from the surface of metal oxide. CONSTITUTION: A polymer thin film is fixed to metal oxide. The polymer thin film is formed by adsorbing dye molecule and reactive adsorbent to the metal oxide with monomer and cross-linking agent. The polymer thin film is a porous thin film.

Description

Metal oxide semiconductor electrode with porous thin film and dye-sensitized solar cell using same and manufacturing method therefor {DYE-SENSITIZED SOLAR CELLS AND MANUFACTURING METHODS THEREOF}

The present invention relates to a dye-sensitized solar cell and a method for manufacturing the same, and more particularly, to a new dye-sensitized solar cell and a method for manufacturing the same, which can prevent photoelectron recombination by trivalent iodine and prevent desorption of dye.

The solar cell device refers to a device that directly generates electricity by using a light-absorbing material that generates electrons and holes when light is irradiated. In 1839, French physicist Becquerel discovered the first photovoltaic that caused a light-induced chemical reaction to generate an electric current, after which a similar phenomenon was found in solids such as selenium.

In 1991, Gratzel, Switzerland, introduced a method of manufacturing a solar cell with photoelectric conversion efficiency of 10% using iodine and iodine salts chemisorbed by Ru (phophyrine) dye on nanocrystalline anatase TiO ₂ and dissolved in a solution electrolyte. It was. The photoelectric conversion efficiency of these dye-sensitized solar cells (“DSSC”) is generally known to be superior to that of solar cells based on amorphous silicon, and is currently the most advanced alternative to silicon diodes. One of the techniques.

Dye-sensitized solar cells consist of a semiconductor electrode made of porous nanoparticle titanium dioxide (TiO ₂ ) on which dye molecules are adsorbed, a counter electrode coated with platinum or carbon, and an electrolyte filled between the semiconductor electrode and the counter electrode. have. In other words, a dye-sensitized solar cell is a solar cell manufactured using a photoelectrochemical reaction by inserting an electrolyte into an inorganic oxide layer such as titanium oxide in which dye is adsorbed between a transparent electrode and a metal electrode.

In general, dye-sensitized solar cells are composed of two electrodes (photoelectrode and counter electrode), inorganic oxides, dyes, and electrolytes. Dye-sensitized solar cells are environmentally friendly because they use environmentally harmless materials / materials, Among the inorganic solar cells, it has high energy conversion efficiency comparable to that of amorphous silicon-based solar cells, and the manufacturing cost is only about 20% of silicon solar cells. 4,927,721 and 5,350,644).

Looking at the driving principle of the dye-sensitized solar cell device, when the light is irradiated to the dye-adsorbed titanium oxide layer, the dye absorbs photons (electron-hole pairs) to form excitons, and the excitons formed are ground states. Is converted to an excited state at. As a result, electrons and hole pairs are separated, and electrons are injected into the titanium oxide layer, and holes move to the electrolyte layer. If an external circuit is installed here, electrons move through the titanium oxide layer through the lead and move from anode to cathode to generate current. The electrons moved to the cathode are reduced by the electrolyte to generate current while continuously moving the electrons in the excited state.

In order to increase the photoelectric conversion efficiency of a dye-sensitized solar cell, it is necessary to first increase the amount of electrons generated by increasing the amount of sunlight absorbed. Since the absorption of sunlight is proportional to the amount of dye adsorbed, the absorption of dye must be increased to increase the absorption of sunlight, and to increase the absorption of dye per unit area, particles of oxide semiconductors are manufactured in nanometer size. The surface area of the oxide semiconductor must be increased. However, there is a limit to improving the photoelectric conversion efficiency of the solar cell in this way.

Photoelectrons are lost through the recombination of electrons delivered to the semiconductor oxide by the dye through the oxidized species present in the solar cell while passing through the semiconductor oxide layer. In particular, the main cause of the recombination reaction in dye-sensitized solar cells using iodine and iodine ions as oxidation-reducing species is the reaction of photoelectrons on the surface of metal oxides with trivalent iodine ions or oxidized dyes.

Accordingly, methods have been developed to block photoelectrons from accessing oxidized species or to prevent oxidized species from accessing photoelectrons. The first method involves introducing ethylene glycol into the hole transport material of p-type semiconductors to chelate lithium ions. Screening electrons approaching TiO ₂ thereby delaying the recombination reaction (Taiho Park, Saif A. Haque, Roberto J. Potter, Andrew B. Holmes, James R. Durrant, Chem. Comm. 2003, 11, 2878. Saif A. Haque, Taiho Park, C. Xu, S. Koops, Neil Schulte, Roberto J. Potter, Andrew B. Holmes, James R. Durrant, Adv.Func. Mater. 2004, 14, 435). .

The second method involves the addition of highly toxic bases, such as tertiary aromatic amines, to the electrolyte to improve the open voltage (MK Nazeeruddin, A. Kay, I. Rodicio and M. Gratzel, J. Am. Chem). Soc., 1993, 115, 6382).

In addition, an example in which an insulating layer is introduced on an exposed surface of a semiconductor oxide layer formed on a semiconductor electrode and an exposed surface of a conductive substrate (Korean Patent Laid-Open Publication No. 10-2008-0029597) and after the surface of the semiconductor electrode is coated with aluminum oxide or another metal oxide Examples of adsorbing dyes (Emilio Palomares, John N. Clifford, Saif A. Haque, Thierry Lutz, and James R. Durrant, J. AM.CEM.SOC. 2003, 125, 475-482. Shlomit Chappel, Si-Guang Chen, and Arie Zaban, Langmuir 2002, 18, 3336-3342).

In addition, a method of preventing leakage of an electrolyte solution by mixing a polymer thin film with an electrolyte solution has been proposed (Korean Patent Publication No. 10-2009-0012911).

However, this method is difficult to control the recombination reaction of the photoelectrons occurring on the surface of the metal oxide, and there is a continuing need for a way to improve this.

In addition, the dye is adsorbed by forming a carboxylate on the surface of the TiO ₂ and this chemical bond is repeated by the chemical equilibrium desorption and adsorption. That is, in the case of manufacturing an element by injecting an electrolyte solution after adsorbing the surface of TiO ₂ using an excess dye solution, the dye molecules are desorbed into the electrolyte solution. Desorption of these dyes is desorbed and dissolved into the electrolyte because they are not adsorbed on the surface of TiO ₂ again by the chemical equilibrium principle, and the dissolved dyes are not known to produce photoelectrons, thereby reducing the efficiency of dye-sensitized solar cells. have. That is, in order to secure long-term stability of the dye-sensitized solar cell, a method is required in which the dye is not desorbed inside the dye-sensitized solar cell or can be adsorbed again even if desorbed.

The problem to be solved by the present invention is to provide a new method that can increase the light efficiency and ensure long-term stability of the metal oxide fuel cell by limiting the access of trivalent iodine ions to the metal oxide surface.

Another problem to be solved in the present invention is to provide a novel way to limit the access of trivalent iodine ions to the metal oxide surface and to prevent the desorption of the dye.

Another problem to be solved by the present invention is to provide a method of improving the light efficiency by dispersing the dye while limiting the access of trivalent iodine ions to the metal oxide surface and preventing the desorption of the dye.

Another problem to be solved by the present invention is to provide a method for fixing a porous thin film on the surface of the metal oxide that can limit the access of trivalent iodine ions to the metal oxide surface and prevent the desorption of fuel.

In order to solve the above problems, the dye-sensitized solar cell according to the present invention is characterized in that the porous thin film formed on the surface of the metal oxide.

In one aspect, the present invention provides a dye-sensitized solar cell including a semiconductor electrode, a counter electrode, and an electrolyte, wherein the semiconductor electrode includes a metal oxide semiconductor and a polymer thin film is formed on a porous thin film to which dye is adsorbed. It is characterized in that the solar cell.

In one aspect, the present invention is characterized in that a polymer thin film is formed on a porous thin film in which a dye containing a metal oxide semiconductor fine particle is adsorbed.

In one aspect, the method of manufacturing a dye-sensitized solar cell is characterized in that a porous thin film is formed on a porous membrane containing metal oxide semiconductor fine particles.

In one aspect, the present invention provides a dye-sensitized solar cell using an iodine / iodide as an oxidation / reduction pair, wherein a porous thin film having a pore less than trivalent iodine ions is formed on a surface of a semiconductor electrode.

In the present invention, the porous thin film is not theoretically limited, but has a low permeability to oxidized species of the oxidation / reduction pair included in the electrolyte, for example, cations that recombine with electrons, for example trivalent iodine ions. For example, the pore size is smaller than that of trivalent iodine ions, thereby inhibiting the access of the oxide species to the oxide semiconductor, thereby reducing the decrease in efficiency due to electron recombination.

In the present invention, the porous thin film is preferably a polymer porous thin film, the polymer porous thin film is fixed to the metal oxide to prevent the desorption of the adsorbed dye.

In the present invention, the porous polymer thin film is preferably fixed to the metal oxide through a material co-adsorbed with the dye on the metal oxide, more preferably, after the dye molecule is adsorbed with the reactive co-adsorbent, the monomer Using a crosslinking agent to copolymerize the monomer and the crosslinking agent on the surface of the metal oxide electrode dye is adsorbed to form a porous polymer thin film.

In the present invention, when the porous polymer thin film is prepared from a mixture of a monomer and a crosslinking agent, one or two or more olefinic monomers having a double bond may be used, and the crosslinking agent may include a compound in which two or more compounds used as monomers are linked. 1 type, or 2 or more types can be used.

In the practice of the present invention, the porous polymer is preferably a cross-linked acrylic polymer, for example, methyl methacrylate, ethyl methacrylate, ethylhexyl acrylate, methyl acrylate crosslinking using a crosslinking agent It may be one polymer.

In addition, when the porous polymer thin film is prepared from a mixture of a monomer and a crosslinking agent, a mixture of an epoxy and an amine compound capable of a crosslinking reaction by a ring-opening reaction of an epoxy and an amine may be used.

 In the present invention, when the porous polymer thin film is prepared from a mixture of a monomer and a crosslinking agent, one or two or more olefinic monomers having a double bond may be used, and the crosslinking agent may be a compound in which two or more kinds of compounds used as monomers are connected. When copolymerizing using one type or two types or more, the azo compound peroxide reaction initiator, light, or heat may be selected or mixed to suit the properties of the monomer and the crosslinking agent. In addition, when the porous polymer thin film is prepared from a mixture of a monomer and a crosslinking agent, an acid or base catalyst may be used when using a mixture of an epoxy and an amine compound capable of a crosslinking reaction by a ring-opening reaction of an epoxy and an amine.

In the present invention, the reactive co-adsorbent includes a carboxyl acid, acyl halide, alkoxysilyl, halide silyl, and phosphorus, which includes a double bond, an epoxy, and an amine capable of adsorbing to the semiconductor metal oxide electrode on one side thereof, including a double bond, an epoxy, and an amine capable of crosslinking at the terminal. The compound represented by general formula (1)-(6) can be used 1 type or in mixture of 2 or more types.

R 1 is hydrogen or an alkyl group having 1-10 carbon atoms, and A is a reactor capable of adsorbing on the surface of a metal oxide, including carboxylic acid, acyl halide, alkoxysilyl, halide silyl, and phosphorus. B is a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, or a person atom. n is a natural number 1-40. m is 0 or a natural number 1-10. D is a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a person atom or a linker containing such an atom. Examples of formula (1) include but-3-enoic acid, pent-4-enoic acid, hex-4-enoic acid, hept-4-enoic acid, non-9-enoic acid, and the like. Examples of general formula (2) include malonic acid monovinyl ester, lactic acid monovinyl ester, heptanedioic acid monovinyl ester, and the like. Examples of general formula (3) include 4-oxo-hex-5-enoic acid, acrylic acid carboxymethyl ester, methacryloyl-4-aminobutyric acid, 6-acryloylamino-hexanoic acid, 9-acrylic Loylamino-nonanoic acid, 6- (2-methyl-acryloylamino) -hexanoic acid, 9- (2-methyl-acryloylamino) -nonanoic acid, 14-acryloyloxy-tetra Decanoic acid, 14- (2-methyl-acryloyloxy-tetradecanoic acid), and the like. Examples of general formula (4) include 4- (4-vinyl-phenyl) butyric acid, 4- (4-vinyl-phenoxy) -propionic acid, 6- (4-vinyl-phenyl) hexyric acid, 6- ( 4-vinyl-phenoxy) -hexanoic acid and the like. Examples of the general formula (5) include 6-amino-hexanoic acid and 8-amino-octanoic acid. Examples of general formula (6) include 6-oxyrenyl-hexanoic acid, 8-oxyrenyl-octanoic acid, and the like.

In the present invention, when the reactive co-adsorbent is an olefin which is a double bond, one or two or more monomers represented by the following general formulas (7) to (10) may be used for crosslinking. In addition, when the reactive coadsorbent is an epoxy, an amine represented by the general formula (11) may be used. When the reactive coadsorbent is an amine, an epoxy represented by the general formula (12) may be used.

Wherein R 1 is hydrogen or an alkyl group of 1-10 carbon atoms, and R 2 is hydrogen, nitrogen, silicon, phosphorus or a terminal group containing such carbon. B is a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, or a person atom. n is 0 or a natural number 1-20. m is 0 or a natural number 1-10. D is a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a person atom or a linker containing such an atom.

In addition, as a crosslinking agent, 1 type (s) or 2 or more types can be used for the compound in which 1 type (s) or 2 or more types are connected by R2 in the compound represented by said General Formula (7)-(12).

In the present invention, the dye-sensitized solar cell including the metal oxide electrode may include one or two or more dye molecules on the conductive first electrode, the metal oxide semiconductor layer formed on the first electrode, and the metal oxide semiconductor layer. And a counter electrode including an adsorbed semiconductor electrode and a metal layer formed on the second substrate.

The present invention injects an electrolyte solution containing an oxidation-reduction derivative between the semiconductor electrode and the counter electrode, or forms a polymer gel electrolyte by applying a polymer gel electrolyte composition including the oxidation-reduction derivative to the semiconductor electrode. It provides a method of manufacturing a dye-sensitized solar cell comprising the step of bonding the second electrode by placing a second electrode thereon.

1 is a cross-sectional view of a dye-sensitized solar cell device fabricated using a metal oxide semiconductor electrode in which a porous polymer thin film is adsorbed with dye molecules according to a preferred embodiment of the present invention, as shown in the preferred embodiment of the present invention. In the dye-sensitized solar cell device manufactured according to the present invention, a first electrode 1002 and a second electrode 1007 are opposed to each other between two transparent substrates, a first substrate 1001 and a second substrate 1008, respectively. An inorganic oxide layer 1003, a dye and reactive material layer 1004, a porous polymer thin film layer 1005 and an electrolyte layer 1006 are interposed between the first electrode 1002 and the second electrode 1007. It has a multilayer thin film form.

The first substrate 1001 is made of glass or a transparent material such as polyethylene terephthalate (PET), polyethylene naphthelate (PEN), polypropylene (PP), polyamide (PI), tri acetyl cellulose (TAC), or the like. And preferably is made of glass.

The first electrode 1002 is an electrode formed of a transparent material on one surface of the first substrate 1001. The first electrode 1002 functions as an anode, and as the first electrode 1002, a material having a lower work function compared to the second electrode 1007 and having transparency and conductivity, Materials can be used. In the present invention, the first electrode 1002 may be applied to the back surface of the first substrate 1001 or coated in a film form by using a sputtering or spin coating method.

In connection with the present invention, a material that can be used as the first electrode 1002 is indium-tin oxide (ITO), fluorine doped tin oxide (FTO), ZnO- (Ga ₂ O ₃ or Al ₂ O ₃ ), SnO ₂ -Sb ₂ O ₃ and the like can be optionally selected, particularly preferably ITO or FTO.

And the inorganic oxide layer 1003 is preferably a transition metal oxide in the form of nanoparticles, for example titanium oxide, scandium oxide, vanadium oxide, zinc oxide, gallium oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide Transition metal oxides such as indium oxide, tin oxide, lanthanide oxide, tungsten oxide and iridium oxide, as well as alkaline earth metal oxides such as magnesium oxide and strontium oxide, aluminum oxide and the like. Materials that can be used as inorganic oxides in the context of the present invention are titanium oxides in the form of nanoparticles.

The inorganic oxide layer 1003 according to the present invention is coated on one surface of the first electrode 1002 and then applied to the first electrode 1002 by heat treatment. In general, the inorganic oxide layer 1003 is coated with a doctor blade method or a screen printing method. The paste including the oxide may be coated on the back surface of the first electrode 1002 with a thickness of about 5-30 μm, preferably 10-15 μm, or a spin coating method, a spray method, or a wet coating method may be used.

Functional layers having several functions are introduced on the inorganic oxide layer 1003 constituting the dye-sensitized solar cell device of the present invention. On the inorganic oxide layer 1003, a porous polymer thin film layer connected with a reactive material in order to minimize the transition of electrons between dye molecules and to delay the recombination reaction of the oxidized species or holes in the electrolyte with the holes ( 1005).

On the other hand, the dye is oxidized after transferring the electrons to the inorganic oxide, but receives the electrons transferred to the electrolyte layer 1006 is reduced to its original state. Accordingly, the electrolyte layer 1006 receives electrons from the second electrode 1007 and transfers them to the dye.

According to the present invention, the photosensitive dye chemically adsorbed to the inorganic oxide layer 1003 may be a dye such as a ruthenium composite as a material capable of absorbing light in the ultraviolet and visible light regions. The photosensitive dye adsorbed on the inorganic oxide layer 1003 includes a photosensitive dye consisting of a ruthenium complex such as ruthenium 535 dye, ruthenium 535 bis-TBA dye, and ruthenium 620-1H3TBA dye, and preferably ruthenium 535 bis- TBA dyes are used. However, any dye having a charge separation function may be used as the photosensitive dye that may be chemisorbed onto the inorganic oxide layer 1003. In addition to the ruthenium dye, xanthene dye, cyanine dye, porphyrin dye, anthraquinone dye And organic dyes and the like can be used.

Conventional methods may be used to adsorb the dye to the inorganic oxide layer 1003, but preferably the dye may be selected from alcohols, nitriles, halogenated hydrocarbons, ethers, amides, esters, ketones, N-methylpyrrolidone, and the like. After dissolving in a solvent, or preferably in a co-solvent of acetonitrile and t-butanol, a method of immersing a photoelectrode coated with the inorganic oxide layer 1003 may be used.

In addition, the electrolyte used in the electrolyte layer 1006 may be a combination of I ₂ and metal iodide or organic iodide (metal iodide or organic iodide / I ₂ ) or a combination of Br ₂ and metal bromide or organic bromide ( Metal bromide or organic bromide / Br ₂ ) can be used as the oxidation / reduction pair.

Li, Na, K, Mg, Ca, Cs, etc. may be used as the metal cation forming the metal iodide or the metal bromide in the electrolyte used according to the present invention, and as the cation of the organic iodide or the organic bromide Ammonium compounds such as imidazolium, tetra-alkyl ammonium, pyridinium, and triazolium are suitable, but are not limited to these compounds. Can be used. Particularly preferably an oxidation / reduction pair combining LiI or imidazolium iodine with I ₂ can be used. Organic halides that can be used as ionic liquids in the electrolytes that can be used according to the invention include n-methylimidazolium iodine, n-ethylimidazolium iodine, 1-benzyl-2-methylimidazolium iodine, 1 -Ethyl3-methylimidazolium iodine, 1-butyl-3-methylimidazolium iodine and the like can be used, with 1-ethyl-3-methylimidazolium iodine being particularly preferred, these being iodine (I ₂ ) It can be used in combination. In the case of using such an ionic liquid, that is, a dissolved salt, a solid electrolyte without using a solvent in the electrolyte composition may be configured.

On the other hand, the second electrode 1007 is an electrode applied to the back surface of the second substrate 1008 and functions as a cathode. The second electrode 1007 may be applied or coated onto the back surface of the second substrate 1008 using a method of sputtering or spin coating.

The material that can be used for the second electrode 1007 is a material having a work function value larger than the material used for the first electrode 1002 and includes platinum (Pt), gold (Au), silver (Ag), and carbon (C). Etc. may be used, and preferably platinum is used. The second substrate 1008 is a transparent material similar to the first substrate 1001, and may be glass or polyethylene terephthalate (PET), polyethylene naphthelate (PEN), polypropylene (PP), polyamide (PI), and tri acetyl (TAC). cellulose) and the like, and may be made of a transparent material such as plastic, preferably made of glass. Looking at the manufacturing process of the dye-sensitized solar cell device manufactured according to a preferred embodiment of the present invention.

First, an inorganic oxide, preferably a colloidal titanium oxide, is applied or cast to a thickness of about 5-30 μm on a first substrate to which the first electrode material is applied, and then fired at a temperature of about 450-550 ° C. sintering to form a photoelectrode in which the first substrate-first electrode-inorganic oxide having organic matters removed thereon is applied / laminated. Subsequently, a dye, for example, a ruthenium-based dye N719 and a reactive co-adsorbent represented by the general formulas (1) to (6) are added to an ethanol solution prepared in advance to adsorb the dye to the prepared inorganic oxide layer. After the preparation, a transparent substrate (for example, a glass substrate coated with FTO or the like, a photoelectrode) coated with an inorganic oxide layer is added to the solution to adsorb the dye and the reactive co-adsorbent.

In the compound represented by the above general formulas (7) to (12), a mixed solution or initiator having a molar ratio of the monomer and the crosslinking agent connected by R2 in the compound represented by the above general formulas (7) to (12) is 0.05-50 The above mixed solution is applied and polymerized by applying heat or light. A dye-sensitized solar cell device according to the present invention is manufactured by bonding a platinum electrode prepared by firing a platinum precursor material on a glass substrate to a semiconductor electrode coated with a porous polymer thin film and injecting an electrolyte solution.

In the dye-sensitized solar cell according to the present invention, the dye molecules and the reactive compound are evenly dispersed in the porous membrane including the metal oxide semiconductor fine particles, and the dye molecules are strongly fixed to the metal oxide surface and can block the access of trivalent iodine. It is composed of a material capable of regenerating a dye by receiving holes from the oxidized dye interposed between the metal oxide semiconductor electrode coated with the porous polymer thin film and the counter electrode and transferring the holes to the counter electrode.

In addition, the porous polymer thin film of the present invention surrounds the surface of the dye-adsorbed metal oxide, thereby minimizing the desorption and recombination reaction of the dye molecules, which is the most important cause of the durability reduction of the device, thereby simultaneously improving the open voltage and the short-circuit current to improve the photoelectric conversion efficiency. Not only is it greatly improved, but also the durability of the device provides a technology for the development of dye-sensitized solar cells with high efficiency, low cost and long-term stability.

1 is a cross-sectional view showing the structure of a dye-sensitized solar cell device manufactured according to the present invention.
2 is a cross-sectional view showing a titanium oxide electrode incorporating a porous polymer thin film prepared according to the present invention.
3 is an enlarged photograph of a cross section of a titanium oxide layer by 150000 times.
FIG. 4 is a photograph of a cross-section of a titanium oxide layer into which a porous polymer thin film prepared according to the present invention is introduced, at a magnification of 150000 times.
5 is a graph comparing thermal (80 ° C.) stability of the device manufactured according to Example 1 and Comparative Example 1 as an example of the durability test.
6 is a graph comparing voltage-current characteristics of Examples 1, 2, 4-8 and Comparative Example 1. FIG.
7 is a graph comparing voltage-current characteristics of Example 3 and Comparative Example 2. FIG.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it is within the scope of the present invention.

Example  One

A composition for forming a TiO ₂ (solaronix) porous film was coated on a transparent glass substrate coated with a florin-doped indium tin oxide having a substrate resistance of 15Ω / □ by using a doctor blade method. After drying, heat treatment was performed at 500 ° C. for 30 minutes to form a porous membrane including TiO ₂ . At this time, the thickness of the prepared porous membrane was about 6㎛. Next, 0.30 mM ruthenium (4,4-dicarboxy-2,2′-bipyridine) ₂ was used as a dye using acetonitrile and tert-butanol (1: 1 by volume) as a solvent. (NCS) was immersed in a 0.30 mM solution of methacryloyl-4-aminobutyric acid for 18 hours as a coadsorbent to adsorb the dye onto the porous membrane. Next, a solution having a molar ratio of methyl methacrylate and 1,6-hexanediol diacrylate of 2 is applied to the first electrode on which the dye and the co-adsorbent are adsorbed onto the porous membrane, and then crosslinked at 80 ° C. for 30 minutes. As shown in the photographs of 6000 magnification and 150000 magnification of the cross section measured by SEM in FIGS. 4 and 5, the porous polymer thin film formed while covering the TiO ₂ particles can be seen.

Platinum paste (solaronix) was applied using a doctor blade method on a florin-doped indium tin oxide coated transparent glass substrate having a substrate resistance of 15Ω / □. After drying, heat treatment was performed at 450 ° C. for 30 minutes to form a catalyst electrode to form a second electrode. A 0.75 mm drill was used to make a hole through the second electrode.

0.6M 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) and 0.03M iodine, 0.10M guani in acetonitrile, valeronitrile (85:15 volume ratio) solvent Guanidinium thiocyanate and 0.5 M 4-tert-butylpyridine are dissolved to prepare an electrolyte solution, and injected into the pores. The battery was prepared.

Example  2

0.8 M of 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) in a solvent of methoxypropionitrile and 0.03 M of iodine, 0.2 M of 4- It is the same as that of Example 1 except for dissolving tert-butylpyridine (4-tert-butylpyridine).

Example  3

In the electrolyte solution of Example 2, a mixed solution having a ratio of methyl methacrylate and 1,6-hexanediol diacrylate of 4 was used as the electrolyte solution. The same procedure as in Example 2 was carried out except that the semi-solid dye-sensitized solar cell was manufactured by crosslinking the electrolyte solution again.

Example  4

It is the same as Example 1 except using the solution whose molar ratio of methyl methacrylate and 1, 6- hexanediol diacrylate is 4.

Example  5

It is the same as Example 1 except using the solution whose molar ratio of methyl methacrylate and 1, 6- hexanediol diacrylate is 0.5.

Example  6

Same as Example 1 except that styrene was used instead of methyl methacrylate.

Example  7

It is the same as Example 1 except using 1, 4- butanediol diacrylate instead of 1, 6- hexanediol diacrylate.

Example  8

Same as Example 1 except that methacryloyl-4-aminorolic acid was used instead of methacryloyl-4-aminobutyric acid as a coadsorbent.

Comparative example  One

A composition for forming a TiO ₂ (solaronix) porous film was coated on a transparent glass substrate coated with a florin-doped indium tin oxide having a substrate resistance of 15Ω / □ by using a doctor blade method. After drying, heat treatment was performed at 500 ° C. for 30 minutes to form a porous membrane including TiO ₂ . At this time, the thickness of the prepared porous membrane was about 6㎛.

Next, 0.30 mM ruthenium (4,4-dicarboxy-2,2′-bipyridine) ₂ was used as a dye using acetonitrile and tert-butanol (1: 1 by volume) as a solvent. The dye was adsorbed onto the porous membrane by immersion in (NCS) solution for 18 hours.

Platinum paste (solaronix) was applied using a doctor blade method on a florin-doped indium tin oxide coated transparent glass substrate having a substrate resistance of 15Ω / □. After drying, heat treatment was performed at 450 ° C. for 30 minutes to form a catalyst electrode to form a second electrode. A 0.75 mm drill was used to make a hole through the second electrode.

0.6M 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) and 0.03M iodine, 0.10M guani in acetonitrile, valeronitrile (85:15 volume ratio) solvent Guanidinium thiocyanate and 0.5 M 4-tert-butylpyridine are dissolved to prepare an electrolyte solution, and injected into the pores. The battery was prepared.

Comparative example  2

0.8M 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide) in a solvent of methoxypropionitrile, 0.03M iodine, 0.2M 4- A mixed solution having a ratio of 4-tert-butylpyridine, methyl methacrylate and 1,6-hexanediol diacrylate of 4 was used as an electrolyte solution. And it is the same as that of the comparative example 1 except having manufactured the semi-solid dye-sensitized solar cell by crosslinking electrolyte solution again.

Example  9

The dye-sensitized solar cell produced in Example 1 was stored at 80 degrees, and taken out at 200 hours, 400 hours, 600 hours, 800 hours, 1000 hours, and 1200 hours, respectively, and the solar cell efficiency was measured.

Comparative example  3

The dye-sensitized solar cell produced by Comparative Example 1 was stored at 80 degrees, and taken out at 200 hours, 400 hours, 600 hours, 800 hours, 1000 hours, and 1200 hours, respectively, and the solar cell efficiency was measured.

The porous polymer thin film of the present invention covers the surface of the dye-adsorbed metal oxide, thereby minimizing the desorption and recombination reaction of the dye molecules, which is the most important cause of the durability reduction of the device, thereby simultaneously improving the open-circuit voltage and the short-circuit current to increase the photoelectric conversion efficiency. In addition to improving the durability of the device, it provides a technology for the development of dye-sensitized solar cells with high efficiency, low cost and long-term stability. In other words, it provides a dye-sensitized solar cell development technology that can realize high efficiency, low cost and long-term stability at the same time.

1001: first electrode substrate 1002: first electrode
1003: inorganic oxide layer 1004: dye and reactive material layer
1005: porous polymer thin film layer 1006: electrolyte layer
1007: second electrode 1008: second electrode substrate

Claims (22)

A dye-sensitized solar cell comprising a semiconductor electrode, a counter electrode and an electrolyte, wherein the semiconductor electrode comprises a metal oxide semiconductor and a polymer thin film is formed on a porous thin film to which dye is adsorbed. The solar cell of claim 1, wherein the polymer thin film is fixed to a metal oxide. The solar cell according to claim 1 or 2, wherein the polymer thin film is formed by adsorbing a dye molecule and a reactive adsorbent onto a metal oxide and then copolymerizing a monomer and a crosslinking agent. The solar cell according to claim 1 or 2, wherein the polymer thin film is a porous thin film. The solar cell according to claim 1 or 2, wherein the polymer thin film is a crosslinked polymer thin film. The metal oxide of claim 1 or 2, wherein the metal oxide is titanium oxide, scandium oxide, vanadium oxide, zinc oxide, gallium oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, or lanthanide oxide. 1 or 2 or more types selected from tungsten oxide, iridium oxide, magnesium oxide, strontium oxide, alkaline earth metal oxide and aluminum oxide. The solar cell of claim 1 or 2, wherein the dye is selected from ruthenium dyes, xanthene dyes, cyanine dyes, porphyrin dyes, and anthraquinone dyes. The solar cell of claim 3, wherein the reactive adsorbent is a reactive coadsorbent co-adsorbed with a dye. The solar cell of claim 8, wherein the reactive co-adsorbent is selected from one or more of the following Formulas (1)-(6):

Wherein R1 is hydrogen or an alkyl group of 1-10 carbon atoms, A comprises at least one of carboxylic acid, acyl halide, alkoxysilyl, halidesilyl and phosphorus, B is carbon atom, nitrogen atom, oxygen atom, silicon atom And n is 1-40 natural number, m is 0 or 1-10 natural number, and D is one or more selected from carbon atom, nitrogen atom, oxygen atom, silicon atom and person atom. The method of claim 9, wherein the reactive co-adsorbent is but-3-enoic acid, pent-4-enoic acid, hex-4-enoic acid, hept-4-enoic acid, non-9-enoic acid, malonic acid mono. Vinyl ester, lactic acid monovinyl ester, heptanedioic acid monovinyl ester, 4-oxo-hex-5-enoic acid, acrylic acid carboxymethyl ester, methacryloyl-4-aminobutyric acid, 6-acryloylamino -Hexanoic acid, 9-acryloylamino-nonanoic acid, 6- (2-methyl-acryloylamino) -hexanoic acid, 9- (2-methyl-acryloylamino) -nonanoic acid, 14-Acryloyloxy-tetradecanoic acid, 14- (2-methyl-acryloyloxy-tetradecanoic acid), 4- (4-vinyl-phenyl) butyric acid, 4- (4-vinyl-phenoxy C) -propionic acid, 6- (4-vinyl-phenyl) hexyric acid, 6- (4-vinyl-phenoxy) -hexanoic acid, 6-amino-hexanoic acid, 8-anino-octanoic acid , Consisting of 6-oxyrenyl-hexanoic acid and 8-oxyrenyl-octanoic acid Group in the solar cell characterized in that the selection of one or two or more of them. The solar cell of claim 9 or 10, wherein the polymer thin film is an acrylic polymer thin film. The method according to claim 1 or 2, wherein the electrolyte uses I ₂ ; and metal iodide, organic iodide, or a mixture thereof; as an oxidation / reduction pair, or the electrolyte is Br ₂ ; and metal bromide , Organic bromide, or a mixture thereof; a solar cell using an oxidation / reduction pair. A metal oxide semiconductor electrode, wherein a polymer thin film is formed on a porous thin film to which a dye containing metal oxide semiconductor fine particles is adsorbed. The metal oxide semiconductor electrode as claimed in claim 13, wherein the polymer thin film is a porous crosslinked thin film. The oxide semiconductor electrode as claimed in claim 13 or 14, wherein the polymer thin film is fixed to a surface of a metal oxide. The oxide semiconductor electrode of claim 13, wherein the polymer thin film is formed by applying a monomer and a crosslinking agent to a metal oxide and copolymerizing the same. The oxide semiconductor electrode of claim 16, wherein the polymer thin film is formed after adsorbing dye molecules and a reactive compound. 18. The oxide semiconductor electrode of claim 17, wherein the polymer thin film is an acrylic polymer thin film. A method for producing a dye-sensitized solar cell, comprising forming a porous thin film on a porous membrane containing metal oxide semiconductor fine particles. 19. The method of claim 18, wherein the porous thin film has a higher permeability to electrons than the oxidized species of the oxidation / reduction pair contained in the electrolyte. 20. The method of claim 18 or 19, wherein the porous thin film is a polymer thin film prepared by applying a monomer to a porous membrane and cross-polymerizing the same. Dye-sensitized solar cell, characterized in that the porous thin film is formed on the surface of the semiconductor electrode having less pores than trivalent iodine ions.

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