KR20100041486A - Gel-type polymer electrolyte comprising ceramic nanofiller for dye-sensitized solarcell, dye-sensitized solarcell comprising the electrolyte and preparation method of the dye-sensitized solarcell - Google Patents

Abstract

PURPOSE: A gel-type polymer electrolyte including a ceramic nano-filler for a dye-sensitized solar cell, the dye-sensitized solar cell including the same and a method for manufacturing the dye-sensitized solar cell are provided to stabilize the solar cell with respect to the change of an external environment by minimizing the volatilization and the leakage of the electrolyte. CONSTITUTION: A transparent conductive oxide layer(120) is formed on a transparent substrate(110). A cathode electrode(100) is formed on the upper side of the transparent conductive oxide layer. The cathode electrode includes a nano-oxide layer(130) on which a dye is absorbed. A anode electrode(200) includes a platinum layer which is formed on the transparent conductive oxide layer. A ceramic nano-filler is interposed between the cathode electrode and the anode electrode.

Description

GEL-TYPE POLYMER ELECTROLYTE COMPRISING CERAMIC NANOFILLER FOR DYE-SENSITIZED SOLARCELL, DYE-SENSITIZED SOLARCELL COMPRISING THE ELECTROLYTE AND PREPARATION METHOD OF THE DYE-SENSITIZED SOLARCELL}

The present invention minimizes the problems of volatilization or leakage of the electrolyte generated in the conventional liquid electrolyte, and when applied to a dye-sensitized solar cell, long-term stability against external environmental changes, and at the same time voltage and light conversion efficiency similar to the conventional liquid electrolyte It relates to a gel polymer electrolyte for dye-sensitized solar cell, a dye-sensitized solar cell and dye-sensitized solar cell comprising the same.

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. As a photoelectrochemical solar cell using an oxide semiconductor electrode made of oxidized titanium oxide particles, it is 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 simpler in manufacturing process, lower in manufacturing cost, and practically usable as compared with a silicon type solar cell, and many studies have been conducted.

1 is a cross-sectional view of a general dye-sensitized solar cell. Referring to FIG. 1, the dye-sensitized solar cell includes a cathode electrode 100, an anode electrode 200, and a liquid electrolyte 300. The negative electrode 100 includes a transparent substrate 110 and a transparent conductive oxide layer (for example, fluorine-doped tin oxide (FTO) or indium tin oxide (ITO) 120) formed on the transparent substrate. A dye is adsorbed onto the porous nano oxide layer 130 on the conductive transparent substrate. The anode electrode 200 is formed of a platinum catalyst which serves to promote a reduction reaction of an electrolyte in a liquid electrolyte on a conductive transparent substrate including a transparent substrate 210 and a transparent conductive oxide layer 220 formed on the transparent substrate. It has a structure consisting of the formed platinum layer 230. In the liquid electrolyte 300, a solution in which an electrolyte is dissolved is generally used. The liquid electrolyte 300 is disposed in the thermoplastic polymer layer 400 that is provided to form a space between the cathode electrode 100 and the anode electrode 200, and both electrodes and It is touched electrochemically.

In the dye-sensitized solar cell, the light conversion process is irradiated light energy is absorbed by the dye of the cathode electrode 100, the dye is activated to generate holes and electrons. The generated electrons are transferred back to the transparent conductive oxide layer 120 through the nano oxide layer 130, and move to the circuit connected to the anode electrode 200 through a circuit connected to the transparent conductive oxide layer 120. It is delivered to the liquid electrolyte 300 again through the anode-based electrode 200. On the other hand, the holes generated with the electrons are passed through the liquid electrolyte 300 is made of a process of recombining with the electrons returned through the anode-based electrode (200).

However, these dye-sensitized solar cells contain a liquid electrolyte solution, the stability problem of the battery module has been raised, especially the liquid electrolyte solution is difficult to seal and there is a problem of volatilization or leakage of the electrolyte due to the rise of the external temperature, so long-term use If so, problems such as lack of electrochemical stability occurs.

In order to solve these problems, recently, inorganic solid electrolytes and polymer solid electrolytes have been developed instead of liquid electrolytes. However, when such solid electrolytes are used, the transfer efficiency of electrons and ions is poor. There is a problem. In addition, although gel polymer electrolytes have been developed to solve the problems of the non-liquid electrolytes, the gel polymer electrolytes developed to date have been improved to some extent with respect to the possibility of volatilization or leakage of the conventional liquid electrolytes. The migration of electrons from the reducing derivatives is difficult and the ionic conductivity is poor, which does not completely improve the problem of photoelectrochemical properties.

In order to solve the problems of the prior art as described above, the present invention minimizes the problems of volatilization or leakage of the electrolyte generated in the conventional liquid electrolyte, while being stable in the long term against external environmental changes when applied to a dye-sensitized solar cell, At the same time, to provide a gel-type polymer electrolyte for a dye-sensitized solar cell comprising a ceramic nano-filler exhibiting a voltage and light conversion efficiency similar to that of a conventional liquid electrolyte, a dye-sensitized solar cell and a method for manufacturing a dye-sensitized solar cell comprising the same. do.

In order to achieve the above object, the present inventors have intensively studied, and the gel polymer electrolyte containing any one or two or more polymer components of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof may be used as a redox liquid electrolyte solution. By minimizing the possibility of volatilization or leakage, it is confirmed that it is stable in the long term against external environmental changes when applied to dye-sensitized solar cells, and at the same time exhibits a voltage and light conversion efficiency similar to that of a conventional liquid electrolyte by adding ceramic nanofillers. Through this, the present invention has been completed.

The present invention provides a gel polymer electrolyte for dye-sensitized solar cells comprising a ceramic nanofiller and at least one polymer component selected from the group consisting of polymer monomers, oligomers, polymers and copolymers thereof.

The gel-type polymer electrolyte for dye-sensitized solar cells comprises a polymer electrolyte, an oligomer thereof, a polymer thereof and a copolymer thereof, at least one polymer component, a photopolymerization initiator, a liquid electrolyte solution comprising a redox derivative and an organic solvent, and a ceramic nanofiller. It can be made, including.

The present invention provides a dye-sensitized solar cell, comprising: (A) a transparent substrate; A transparent conductive oxide layer formed on the transparent substrate; And a cathode electrode formed on the transparent conductive oxide layer and including a nano oxide layer to which dye is adsorbed; (B) a transparent substrate; A transparent conductive oxide layer formed on the transparent substrate; And a platinum layer formed on the transparent conductive oxide layer. And (C) a gel polymer electrolyte interposed between the cathode electrode and the anode electrode, comprising at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof and a ceramic nanofiller. It provides a dye-sensitized solar cell comprising a gel polymer electrolyte coating layer formed from.

In another aspect, the present invention provides a method for manufacturing a dye-sensitized solar cell, the first step of manufacturing a cathode electrode; A second step of manufacturing an anode electrode; A gel-type polymer electrolyte for dye-sensitized solar cells comprising a ceramic nanofiller and at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof on a surface of the prepared cathode or anode electrode A third step of coating and thermosetting or ultraviolet curing to form a gel polymer electrolyte coating layer; And a fourth step of attaching a cathode-based electrode or an anode-based electrode in which the gel polymer electrolyte coating layer is formed in the third step.

Gel-type polymer electrolyte for dye-sensitized solar cells comprising a polymer monomer or a polymer component polymerized therefrom and a ceramic nanofiller according to the present invention, by minimizing the problem of volatilization or leakage of the electrolyte generated in the conventional liquid electrolyte, When applied to a battery, it has long-term stability against environmental changes such as an external temperature rise, and at the same time, it has excellent photoelectrochemical characteristics which exhibit similar voltage and light conversion efficiency as in a conventional liquid electrolyte.

The present invention minimizes the problem of volatilization or leakage of the electrolyte generated in the conventional liquid electrolyte, and when applied to the dye-sensitized solar cell long-term stability against external environmental changes, while at the same time similar voltage and light conversion in the conventional liquid electrolyte It relates to a gel polymer electrolyte for dye-sensitized solar cells exhibiting efficiency, a dye-sensitized solar cell and dye-sensitized solar cell comprising the same.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The gel polymer electrolyte for dye-sensitized solar cells of the present invention comprises a ceramic nanofiller as one or more polymer components and additives selected from the group consisting of polymer monomers, oligomers thereof, polymers and copolymers thereof.

More specifically, the gel polymer electrolyte for dye-sensitized solar cells of the present invention is a liquid electrolyte consisting of at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof, and an oxidation-reducing derivative and an organic solvent. It comprises a ceramic nanofiller.

The polymer component may be selected from a monomer which is a polymer, an oligomer thereof, a polymer thereof, or a copolymer thereof, and the polymer monomer may include polyacrylonitrile, polyethylene oxide, polymethyl methacrylate, polyurethane, and the like. Among them, polyacrylonitrile oligomers are most preferably used. Polyacrylonitrile-based polymers have excellent elasticity compared to polyethylene oxide-based polymers, and thus have a peak of excellent bonding properties with electrodes.

In addition, the polymer component is preferably contained in 5 to 40% by weight of the gel polymer electrolyte of the present invention. When the content is less than 5% by weight, it is difficult to form the gel polymer electrolyte as a coating layer. When the content is more than 40% by weight, the ion conductivity is lowered and the light conversion efficiency is lowered.

The liquid electrolyte is composed of an oxidation-reduction derivative and an organic solvent, and a normal oxidation-reduction electrolyte consisting of a halogen group anion such as iodine or bromine and a counter metal cation can be used.

Lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salt, imidazolium salt or pyridinium salt may be used as the redox derivative.

As the organic solvent, acetonitrile, 3-methoxypropionitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran or gamma-butyrolactone may be used.

The liquid electrolyte is preferably contained in 55 to 90% by weight in the gel polymer electrolyte of the present invention. When the content is less than 55% by weight, the ion conductivity is lowered, the light conversion efficiency is greatly reduced, and when the content exceeds 90% by weight it is difficult to form a gel polymer electrolyte as a coating layer.

The ceramic nanofiller is added to the gel polymer electrolyte to improve the light conversion efficiency by increasing the ion conductivity in the electrolyte. In the case of the polymer electrolyte, the polymer matrix is densely adhered, making the charge transfer ions difficult to move, and thus the ion conductivity decreases.However, by adding the ceramic nanofiller, the ceramic nanofiller makes the dense structure of the polymer mexics coarse to move the ion. It is easy to improve ion conductivity. As the ceramic nanofiller, for example, titanium oxide, aluminum oxide, zirconium oxide, tin oxide and the like can be preferably used.

The ceramic nanofiller is preferably contained in 2 to 10% by weight in the gel polymer electrolyte of the present invention. If the content is less than 2% by weight, the ion conductivity is lowered, the light conversion efficiency is greatly reduced, if the content exceeds 10% by weight because the polymer does not form a matrix there is a problem that can not be evenly coated.

The gel polymer electrolyte including the above components is advantageous for commercialization because it can secure long-term stability by minimizing the problem of volatilization or leakage of the electrolyte generated in the conventional liquid electrolyte.

Figure 2 shows a cross-sectional view of the dye-sensitized solar cell according to an embodiment of the present invention.

As shown in FIG. 2, the dye-sensitized solar cell according to the embodiment of the present invention includes (A) an anode electrode 100, (B) an anode electrode 200, and (C) the cathode electrode and an anode. It comprises a gel polymer electrolyte coating layer 500 interposed between the system electrode.

(A) The cathode electrode 100 includes a transparent substrate 110; A transparent conductive oxide layer 120 formed on the transparent substrate; And a nano oxide layer formed on the transparent conductive oxide layer and having a dye adsorbed thereon.

The transparent substrate 110 is polyethersulfone, polyacrylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate and cellulose acetate propio It may be a plastic material or a glass material containing at least one selected from the group consisting of nates.

The transparent conductive oxide layer 120 is a layer formed from fluorine-doped indium tin oxide (FTO) or indium tin oxide (ITO).

The nano oxide layer 130 is formed from a composition containing at least one metal oxide selected from the group consisting of titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ) and zinc oxide (ZnO), and dyes are adsorbed. Layer. The nano oxide layer 130 preferably has a thickness of 5 to 30 μm.

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-based 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.

(B) the anode electrode 200 includes a transparent substrate 210; A transparent conductive oxide layer 220 formed on the transparent substrate; And a platinum layer 230 formed on the transparent conductive oxide layer.

The transparent substrate 210 and the transparent conductive oxide layer 220 are the same as those mentioned in the cathode electrode, and the platinum layer 230 is a layer formed from a platinum catalyst that serves to promote a reduction reaction of the electrolyte.

(C) the gel polymer electrolyte coating layer 500 is disposed between the negative electrode 100 and the positive electrode 200, at least one selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof. A layer formed from a gel polymer electrolyte containing a polymer component and a ceramic nanofiller.

The gel polymer electrolyte includes at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof, a liquid electrolyte solution comprising a redox derivative and an organic solvent, and a ceramic nanofiller.

As described above, the dye-sensitized solar cell including the cathode electrode 100, the anode electrode 200, and the gel polymer electrolyte coating layer 500 includes a nano oxide layer on which the dye of the anode electrode 100 is adsorbed ( 130 and the platinum layer 230 of the anode electrode 200 are disposed to face each other, and a gel polymer electrolyte coating layer 500 is disposed between the cathode electrode 100 and the anode electrode 200. Has a structure. As such, the dye-sensitized solar cell of the present invention includes a gel polymer electrolyte coating layer 500 to minimize the possibility of volatilization or leakage of the redox-based liquid electrolyte solution, and the gel polymer electrolyte coating layer 500 may contain a kind of electrolyte solution. By acting as a retardation, it is stable and lifespan is improved compared with the conventional solar cell containing only liquid electrolyte solution. In addition, by including the ceramic nano-filler, the ion conductivity is increased to improve the photoelectric efficiency.

Method for producing a dye-sensitized solar cell according to the present invention comprises the first step of manufacturing a negative electrode; A second step of manufacturing an anode electrode; A gel-type polymer electrolyte for dye-sensitized solar cells comprising a ceramic nanofiller and at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof on a surface of the prepared cathode or anode electrode Applying and forming a gel polymer electrolyte coating layer including ceramic nanofiller; And a fourth step of attaching a cathode electrode or an anode electrode on which the gel polymer electrolyte coating layer including the ceramic nanofiller is formed in the third step.

Hereinafter, although the manufacturing method of the dye-sensitized solar cell of this invention is demonstrated in detail, this invention is not limited only to the following description.

The first step of manufacturing a cathode-based electrode includes the steps of preparing a transparent substrate; Forming a transparent conductive oxide layer on the prepared transparent substrate; Forming a nano oxide layer by applying a composition including a metal oxide on top of the formed transparent conductive oxide layer; And adsorbing the dye by applying a solution in which the dye is dissolved in the formed nano oxide layer. Specifically, first, after preparing a transparent substrate, indium tin oxide or indium tin oxide doped with fluorine, which is a transparent conductive oxide, is adhered to the upper portion of the transparent substrate by using an adhesive or by coating a coating film by sputtering to form a transparent conductive oxide. A layer can be formed. Next, in order to form a nano oxide layer, after preparing a coating composition comprising at least one metal oxide selected from the group consisting of titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ) and zinc oxide (ZnO), The coating composition may be applied to the upper portion of the formed transparent conductive metal layer by a doctor blade method, and thermally treated at a temperature of 400 to 500 ° C. for 10 to 60 minutes to form a nano oxide layer having a thickness of 5 to 30 μm. In this case, the step of forming the nano oxide layer may be repeated one or more times to form a nano oxide layer having a desired thickness. Next, in order to adsorb the dye to the metal oxide of the formed nano oxide layer, the dye is dissolved in a solvent to prepare a dye solution having a concentration of 0.01 to 5 μM, and then the substrate on which the nano oxide layer is formed is 5 to 5. The dye may be adsorbed by drying for 72 hours and then drying.

The second step of manufacturing the bipolar electrode includes the steps of preparing a transparent substrate; Forming a transparent conductive oxide layer on the prepared transparent substrate; And forming a platinum layer on the formed transparent conductive oxide layer. Specifically, first, after preparing a transparent substrate, indium tin oxide or indium tin oxide doped with fluorine, which is a transparent conductive oxide, is adhered to the upper portion of the transparent substrate using an adhesive or coated with a sputtering method to form a transparent conductive layer. An oxide layer can be formed. Next, after the solution in which the platinum is dissolved on the upper portion of the transparent conductive oxide layer is dropped, the platinum layer may be formed by heat treatment at 400 to 600 ° C. for 10 to 60 minutes. In this case, the platinum layer may be formed using a sputtering method, a chemical vapor deposition method, a vapor deposition method, a thermal oxidation method, an electrochemical deposition method and the like.

The third step of forming a gel polymer electrolyte coating layer comprising a ceramic nano-filler, at least one selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof on the surface of the prepared cathode or anode electrode A gel polymer electrolyte comprising a ceramic nanofiller for a dye-sensitized solar cell including a polymer component and a ceramic nanofiller is coated and thermally cured to form a gel polymer electrolyte coating layer including the ceramic nanofiller. Specifically, after preparing a liquid electrolyte consisting of a redox derivative and an organic solvent, a polymer component and a ceramic nanofiller are added thereto to prepare a gel polymer electrolyte. The gel polymer electrolyte prepared was applied to the surface of the nano-oxide layer to which the dye of the anode electrode prepared in the first step was adsorbed or the platinum layer of the anode electrode prepared in the second step by screen printing method, and 10 to 1 hour. Heat may be applied to form a gel polymer electrolyte coating layer.

In the fourth step of attaching the cathode electrode and the anode electrode, the cathode electrode in which the gel polymer electrolyte coating layer is formed in the third step and the anode electrode manufactured in the second step are attached or the cathode manufactured in the first step. In the third step, attaching the anode-based electrode on which the gel polymer electrolyte coating layer including the ceramic nanofiller is formed is formed. Specifically, the conductive surfaces of the cathodic electrode and the anodic electrode are brought inward, and are attached so as to face each other. After forming a 20-100 μm-thick thermoplastic polymer layer made of SURLYN (manufactured by Du Pont) between the cathode electrode and the anode electrode, it is maintained at a temperature of 120 to 140 ° C. for 1 to 2 minutes to provide two electrodes. It can be sealed.

The dye-sensitized solar cell manufactured by the above method includes a gel polymer electrolyte coating layer including a ceramic nanofiller, wherein the gel polymer electrolyte coating layer minimizes volatilization of an electrolyte that performs oxidation-reduction and fixes a liquid electrolyte solution. It can act as a delay. Therefore, it is stable for a long time against environmental changes such as external temperature increase, and can exhibit photoelectrochemical characteristics similar to those in a liquid electrolyte.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

Example

(1) A transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared. Applying a coating composition comprising titanium dioxide on the transparent conductive oxide layer of the substrate by the doctor blade method, and heat-treated at 500 ℃ for 30 minutes, so that the contact and filling between the nano-sized metal oxide is made to about 8 A nano oxide layer having a thickness of μm was formed. Subsequently, a coating composition including titanium dioxide was applied to the upper portion of the nano oxide layer by the same method, and heat-treated at a temperature of 500 ° C. for 30 minutes to form a nano oxide layer having a thickness of about 15 μm. A 0.2 mM ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate dye solution was prepared. The substrate having the nano oxide layer formed thereon was supported for 24 hours and then dried to adsorb a dye to the nano-sized metal oxide to prepare a cathode electrode.

(2) A transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared. A 2-propanol solution in which chloroplatinic acid (H ₂ PtCl ₆ ) was dissolved was dropped on the transparent conductive oxide layer of the substrate, and then thermally treated at 450 ° C. for 30 minutes to form a platinum layer, thereby preparing an anode-based electrode.

(3) 0.1 M LiI, 0.05 M I ₂ , 0.3 M 1,2-dimethyl-3-propyl-imidazolium iodide (DMPII), 0.5 M 2- (dimethylamino) -pyridine, 0.5 M 5-chloro-1-ethyl-2-methylimidazole was dissolved in a mixed solution of 3 µl of ethylene carbonate and 7 µl of gamma-butyrolactone to prepare a liquid electrolyte. A gel polymer electrolyte having a total content of 100% by weight was prepared by adding 30% by weight of polyacrylonitrile and 5% by weight of titania nanofiller. The gel polymer electrolyte was coated on the platinum layer of the positive electrode, coated by screen printing, and thermally cured in an oven at 100 ° C. for 1 hour to form a gel polymer electrolyte coating layer.

(4) After the nano-oxide layer of the prepared cathode electrode and the gel polymer electrolyte coating layer of the anode electrode were opposed to each other, a thermoplastic polymer layer having a thickness of about 60 µm made of SURLYN (manufactured by Du Pont) was formed. The dye-sensitized solar cell was manufactured by attaching and sealing two electrodes by keeping in an oven at 130 ° C. for 2 minutes.

Comparative Example 1

The same method as in Example 1 was performed except that the titania nanofiller was not used in Example 1.

Comparative Example 2

The same process as in Example 1 was performed except that only the liquid electrolyte solution was added without forming a gel electrolyte layer in Example 1.

Test Example

In order to evaluate the light conversion efficiency of the dye-sensitized solar cells prepared in Examples and Comparative Examples, the photovoltaic characteristics were observed by measuring the photovoltage and the photocurrent in the following manner, and the current density (I _sc ) obtained therefrom, The light conversion efficiency η _e was calculated using Equation 1 using the voltage V _oc and the fill factor ff.

At this time, 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.

η _e = (V _oc × I _sc × ff) / (P _ine )

In Equation 1, (P _ine ) represents 100 ㎽ / ㎠ (1 sun).

The values measured as above are shown in Table 1 below.

division Current density (㎃ / cm ² ) Voltage (V) Fill factor Optical conversion efficiency (%) Example 1 10.585 0.787 0.581 4.850 Comparative Example 1 9.735 0.796 0.572 4.438 Comparative Example 2 10.964 0.764 0.610 5.115

As shown in Table 1, the dye-sensitized solar cell comprising a coating layer formed from the gel polymer electrolyte containing the ceramic nanofillers of Examples 1 to 3 according to the present invention does not include a titania nanofiller, which has been conventionally used. Compared with the dye-sensitized solar cell of 1, the current density was increased and the light conversion efficiency was confirmed to be improved. In addition, it can be confirmed that the photoelectric conversion efficiency is comparable to that of the dye-sensitized solar cell including the liquid electrolyte solution of Comparative Example 2.

1 is a cross-sectional view of a general dye-sensitized solar cell.

2 is a cross-sectional view of a dye-sensitized solar cell according to an embodiment of the present invention.

Explanation of symbols on the main parts of the drawings

100: cathode electrode 110, 210: transparent substrate

120,220: transparent conductive oxide layer 130: nano oxide layer

200: anode electrode 230: platinum layer

300: liquid electrolyte 400: thermoplastic polymer layer

500: gel polymer electrolyte coating layer containing a ceramic nanofiller

Claims (17)

A gel-type polymer electrolyte for dye-sensitized solar cells comprising a ceramic nanofiller and at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof. The method of claim 1, A gel-type polymer electrolyte for dye-sensitized solar cells comprising at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof, and a copolymer thereof, a liquid electrolyte comprising a redox derivative and an organic solvent, and a ceramic nanofiller. The method of claim 2, 5 to 40% by weight of the polymer component, 55 to 90% by weight of the liquid electrolyte, and 2 to 10% by weight of the ceramic nanofiller, based on the total content of the gel polymer electrolyte. The method of claim 2, The polymer monomer is a gel polymer electrolyte for dye-sensitized solar cells selected from the group consisting of polyacrylonitrile, polymethyl methacrylate, polyethylene oxide and polyurethane. The method of claim 2, The redox derivative is 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, The organic solvent is a gel polymer electrolyte for dye-sensitized solar cells selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran and gamma-butyrolactone. The method of claim 2, The ceramic nanofiller is a gel polymer electrolyte comprising a ceramic nanofiller for dye-sensitized solar cells made of a ceramic selected from the group consisting of titanium oxide, aluminum oxide, tin oxide and zirconium oxide. As a dye-sensitized solar cell, (A) a transparent substrate; A transparent conductive oxide layer formed on the transparent substrate; And a cathode electrode formed on the transparent conductive oxide layer and including a nano oxide layer to which dye is adsorbed; (B) a transparent substrate; A transparent conductive oxide layer formed on the transparent substrate; And a platinum layer formed on the transparent conductive oxide layer. And (C) a gel polymer electrolyte disposed between the negative electrode and the positive electrode and comprising at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof and a ceramic nanofiller Dye-sensitized solar cell comprising a gel polymer electrolyte coating layer formed. The method of claim 7, wherein The transparent conductive oxide layer is a dye-sensitized solar cell is a layer formed from fluorine-doped indium tin oxide or indium tin oxide. The method of claim 7, wherein The nano oxide layer is a dye-sensitized solar cell is a layer formed from a composition comprising at least one selected from the group consisting of titanium dioxide, tin dioxide and zinc oxide. The method of claim 7, wherein The dye adsorbed on the nano oxide layer is one selected from the group consisting of ruthenium complex, xanthine dye, cyanine dye, basic dye, porphyrin compound, azo dye, phthalocyanine compound, anthraquinone dye and polycyclic quinone dye. Ideal dye-sensitized solar cell. The method of claim 7, wherein The gel polymer electrolyte coating layer is a dye-sensitized composition comprising a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof, at least one polymer component, a liquid electrolyte consisting of an oxidation-reducing derivative and an organic solvent, and a ceramic nanofiller. Dye-sensitized solar cell is a layer formed from a gel polymer electrolyte for solar cells. The method of claim 11, The liquid electrolyte comprises an oxidation-reduction derivative and an organic solvent, The redox derivative is 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, The organic solvent is a dye-sensitized solar cell selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran and gamma-butyrolactone. As a manufacturing method of a dye-sensitized solar cell, A first step of manufacturing a cathode electrode; A second step of manufacturing an anode electrode; A gel-type polymer electrolyte for dye-sensitized solar cells comprising a ceramic nanofiller and at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof on a surface of the prepared cathode or anode electrode A third step of coating and thermosetting or ultraviolet curing to form a gel polymer electrolyte coating layer; And Method for manufacturing a dye-sensitized solar cell comprising a fourth step of attaching a negative electrode or a positive electrode having a gel polymer electrolyte coating layer formed in a third step. The method of claim 13, The first step of manufacturing a cathode electrode, Preparing a transparent substrate; Forming a transparent conductive oxide layer by applying indium tin oxide or indium tin oxide doped with fluorine on the prepared transparent substrate; Forming a nano oxide layer on the formed transparent conductive oxide layer by applying a composition including at least one selected from the group consisting of titanium dioxide, tin dioxide and zinc oxide; And Method of manufacturing a dye-sensitized solar cell comprising the step of adsorbing the dye by applying a solution in which the dye is dissolved in the formed nano oxide layer. The method of claim 13, The second step of manufacturing a bipolar electrode, Preparing a transparent substrate; Forming a transparent conductive oxide layer by applying indium tin oxide or indium tin oxide doped with fluorine on the prepared transparent substrate; And Method of manufacturing a dye-sensitized solar cell comprising the step of forming a platinum layer on top of the formed transparent conductive oxide layer. The method of claim 13, The gel polymer electrolyte is a dye-sensitized embodiment comprising at least one polymer component selected from the group consisting of a polymer monomer, an oligomer thereof, a polymer thereof and a copolymer thereof, a liquid electrolyte consisting of an oxidation-reducing derivative and an organic solvent, and a ceramic nanofiller. Method for producing a battery. The method of claim 13, The third step of forming the gel polymer electrolyte coating layer is a step of applying the gel polymer electrolyte by the screen printing method, the step of performing heat curing in an oven at 100 ℃.

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