KR101407894B1 - Dye solar cell with chemically bonded co-adsorbent and method of manufacturing the same - Google Patents

Abstract

Disclosed are a dye-sensitized solar cell with a co-adsorbent whose chemical bond is enhanced and a manufacturing method thereof. The method for manufacturing the dye-sensitized solar cell with the co-adsorbent whose chemical bond is enhanced according to the present invention comprises: S1, a step of forming a photoelectrode by absorbing a dye and the co-adsorbent with dipole moment on a porous layer including oxide semiconductor particles formed on one side of a substrate; S2, a step of forming a relative electrode composed of a metallic material at an upper part of the substrate having a conductive oxide layer composed of the oxide semiconductor particles; and S3, a step of preparing a dye-sensitized solar cell module by arranging the photoelectrode spaced apart from the relative electrode while facing each other, injecting the electrolyte and sealing it. By this means, the present invention may have more intensified corrosion resistance against the electrolyte, may prevent back electron transfer reaction by being effectively absorbed on the titanium oxide surface, and may improve dye aggregation.

Description

TECHNICAL FIELD [0001] The present invention relates to a dye-sensitized solar cell having a co-adsorbent enhanced in chemical bonding and a method of manufacturing the dye-

The present invention relates to a dye-sensitized solar cell provided with a co-adsorbent having enhanced chemical bonding and a method for producing the dye-sensitized solar cell. The dye-sensitized solar cell has corrosion resistance to an electrolyte and effectively adsorbs on the surface of titanium dioxide to form a back electron transfer reaction The present invention relates to a dye-sensitized solar cell provided with a co-adsorbent which is capable of preventing cracking of a dye and capable of improving the densification of a dye, and a method for producing the dye-sensitized solar cell.

Solar cells are electricity generation devices that convert solar energy into electric energy by photoelectric effect. Silicon solar cells, compound semiconductor solar cells, laminated solar cells, nano solar cells, etc., Has attracted attention because it is possible to manufacture a cell having a lower manufacturing cost and superior cell transparency and flexibility as compared with a conventional silicon solar cell.

The most basic structure of such a dye-sensitized solar cell can be divided into a photo-electrode coated with nanoparticles containing titanium dioxide as a main component, an electrolyte, and a platinum counter electrode, and titanium dioxide nanoparticles coated on the photo- Is adsorbed on the surface of the substrate.

When the photo-electrode coated with a semiconductor such as titanium dioxide is immersed in the dye solution, the carboxyl group of the dye chemically bonds with the semiconductor, and the dye is adsorbed on the surface of the semiconductor and receives light to produce electrons. When the dye is adsorbed on the surface of the semiconductor, the dye can not be completely deposited on the surface of the semiconductor, but only about 70% of the surface of the semiconductor is adsorbed and about 30% is exposed to the electrolyte. When the surface directly contacts the electrolyte of the dye-sensitized solar cell, the electron recombination occurs, and electrons generated from the dye flow into the electrolyte without flowing to the electrode through the semiconductor. Such an electron flow is not suitable for driving the solar cell There was a problem that it affected.

The present applicant has been studying a solar cell having a silane-coupling co-adsorbent (Korean Patent Application No. 2012-31014), but it has been found that the chemical bond is further strengthened and the corrosion resistance to prevent leakage to the electrolytic solution is stronger The need for technology remains.

Accordingly, the first technical problem to be solved by the present invention is to provide a titanium oxide which has a stronger corrosion resistance against an electrolyte and can effectively adsorb to the surface of titanium dioxide to prevent a back electron transfer reaction and improve the aggregation of dyes And a dye-sensitized solar cell having a co-adsorbent with enhanced chemical bonding that can be used.

The second technical problem to be solved by the present invention is to provide a titanium oxide which has a stronger corrosion resistance against an electrolyte and can effectively adsorb on the surface of titanium dioxide to prevent a back electron transfer reaction and improve the aggregation of dyes The present invention provides a method for producing a dye-sensitized solar cell having a co-adsorbent with enhanced chemical bonding.

SUMMARY OF THE INVENTION In order to solve the first technical problem described above, the present invention provides a light emitting device comprising a substrate on which a conductive film is stacked, a metal oxide layer coated on the conductive film, and a mixture of a dye adsorbed on the metal oxide layer and a molecule having a dipole moment A counter electrode having a second substrate disposed on a surface opposite to the optical electrode and having a conductive film and a platinum layer stacked in this order on the opposed surface, And a sealing member disposed along the rim and sealing the electrode, and an electrolyte injected into a space separated from the photoelectrode and the counter electrode.

According to an embodiment of the present invention, the molecule may have at least one functional group selected from the group consisting of a diphenylphosphino group and a diphenyl ketone group.

According to another embodiment of the present invention, the molecule is selected from the group consisting of 2-Hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone, 2- (Diphenylphosphino) ethyl-dimethylethoxy silane and 2- (Diphenylphosphino) ethyltriethoxy silane It can be at least one.

According to another embodiment of the present invention, the dye is a ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate (ruthenium dithiocyanate 2,2'-bipyridyl- dicarboxylate.

According to another embodiment of the present invention, the dye layer may further include an inclusion compound.

According to another embodiment of the present invention, the entraining compound is selected from the group consisting of deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, polyethylene oxide, cholic acid, crown ether, cyclodextrin, Or polyethylene oxide.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: (a) forming a photoelectrode by adsorbing a dye and a co-adsorbent having a dipole moment on a porous layer including oxide semiconductor fine particles formed on one surface of a substrate; A counter electrode made of a metal material is formed on a substrate having a conductive oxide layer made of oxide semiconductor particles, a step S2 of arranging the counter electrode and the counter electrode so as to face each other, injecting and sealing the electrolyte, And a step S3 of preparing a dye-sensitized solar cell having a chemical bond.

According to an embodiment of the present invention, the co-adsorbent may be a compound having at least one functional group selected from the group consisting of a diphenylphosphino group and a diphenyl ketone group.

According to another embodiment of the present invention, the co-adsorbent is selected from the group consisting of 2-Hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone, 2- (Diphenylphosphino) ethyl-dimethylethoxy silane and 2- (Diphenylphosphino) ethyltriethoxy silane At least one selected.

According to another embodiment of the present invention, the dye is a ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate (ruthenium dithiocyanate 2,2'-bipyridyl- dicarboxylate.

According to another embodiment of the present invention, the step S1 may include the step S11 of adding an inclusion compound.

According to another embodiment of the present invention, the entraining compound is selected from the group consisting of deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, polyethylene oxide, cholic acid, crown ether, cyclodextrin, Or polyethylene oxide.

INDUSTRIAL APPLICABILITY According to the dye-sensitized solar cell having a chemical bond-enhanced co-adsorbent according to the present invention and its manufacturing method, the dye-sensitized solar cell of the present invention has stronger corrosion resistance against the electrolyte and also effectively adsorbs on the titanium dioxide surface, transfer reaction can be prevented and dye aggregation can be improved.

1 is a cross-sectional view of a solar cell according to the present invention,
FIG. 2 is a view showing the manufacturing method of the solar cell according to the present invention in order.

These and other objects, features and other advantages of the present invention will become more apparent by describing in detail preferred embodiments of the present invention with reference to the accompanying drawings.

Hereinafter, a dye-sensitized solar cell having a chemical bond-enhanced co-adsorbent according to an embodiment of the present invention and a method of manufacturing the same will be described in detail.

The present invention relates to a photoelectrode comprising a substrate on which a conductive film is laminated, a metal oxide layer coated on the electroconductive film, and a dye layer made of a mixture of a dye adsorbed on the metal oxide layer and a molecule having a dipole moment, A counter electrode on which a second substrate is disposed on a surface facing away from the light electrode and a conductive film and a platinum layer are sequentially laminated on the opposing face, a sealing member disposed and sealed along the edge of the photo electrode and the counter electrode, And an electrolyte solution injected into a space between the photoelectrode and the counter electrode.

This will be described with reference to FIG. 1 attached hereto. FIG. 1 is a cross-sectional view of a solar cell according to the present invention. The solar cell of the present invention includes a substrate 110 on which a conductive film 120 is stacked, a metal oxide layer 130 coated on the conductive film, And a dye layer 140 made of a mixture of a dye adsorbed on the metal oxide layer and a molecule having a dipole moment; and a second electrode 140 on a surface opposite to the light electrode 100, A counter electrode 200 in which a conductive film 210 and a conductive layer 220 and a platinum layer 230 are sequentially stacked on an opposing face of the counter electrode 200 and a counter electrode 200 disposed along the edge of the counter electrode 200 and the counter electrode 200 And an electrolyte 500 injected into a space between the photoelectrode and the counter electrode is electrically connected to both electrodes 100 and 200 so that an external circuit And a conductive line which is a passage through which electricity is conducted to the system.

Here, the substrate 110 should have a transparency in relation to the solar cell to support the solar cell and to transmit the sunlight. In general, a glass material or a polymer film may be used. In the conductive film 120, Is a conductive layer formed by depositing a material such as indium tin oxide (ITO) or fluorine tin oxide (FTO) on the substrate 110 by physical vapor deposition or chemical vapor deposition.

The metal oxide layer 130 may be formed by applying a coating composition containing an oxide semiconductor particle such as TiO ₂ , SnO ₂ , ZnO, WO ₃ , Nb ₂ O _5, or TiSrO ₃ , followed by heat treatment.

In addition, the dye layer 140 is formed by being adsorbed on the metal oxide layer 130 as a mixture of a dye and a molecule having a dipole moment, and the dye is not particularly limited, but may be ruthenium dithiocyanate Ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate, and the molecule having the above dipole moment may be used in particular, Refers to a dipole moment that exhibits a repulsive force between opposite charges and a repulsive force between the opposite charges to distinguish it from a covalent bond, a hydrogen bond, a van der Waals bond, or an ionic bond, and the binding force to the metal oxide layer 130 In this sense, it is possible to strongly bond with the photo-electrode nano-scale titanium dioxide (TiO ₂ ) of the dye-sensitized solar cell, so that the possibility of dissolving in the electrolyte is very small, It is adsorbed on the surface of titanium oxide to prevent back electron transfer reaction.

Such a molecule is particularly characterized by having at least one functional group selected from the group consisting of diphenylphosphino group and diphenylketone group, more preferably 2-hydroxy-4- (3-methyldiethoxyl-proxy Diphenylketone, 2- (diphenylphosphino) ethyl-dimethylethoxy silane and 2- (diphenylphosphino) ethyl-dimethylethoxy silane. And 2- (diphenylphosphino) ethyltriethoxy silane (Diphenylphosphino) ethyltriethoxy silane.

In addition, it is possible to use an entrapping compound for preventing unnecessary binding, non-adsorption, and clustering with each other or mutually by the dye molecules to be used, such as a co-adsorbent and a co-adsorbent. Preferable examples thereof include deoxycholic acid, At least one selected from the group consisting of deoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, polyethylene oxide, cholic acid, crown ether, cyclodextrin, calixarene or polyethylene oxide may be used, Can be evaporated through a normal heat treatment or drying process.

Meanwhile, a method of manufacturing a dye-sensitized solar cell having a chemical bond-enhanced co-adsorbent according to the present invention includes a step of adding a dye to a porous layer containing fine oxide semiconductor particles formed on one surface of a substrate, Forming a counter electrode made of a metal material on the substrate having the conductive oxide layer made of the oxide semiconductor fine particles, forming a counter electrode having at least one functional group selected from the group consisting of Sn, And a step S3 of arranging the photoelectrode and the counter electrode so as to face each other and injecting and sealing the electrolyte.

This will be described with reference to FIG. 2 attached hereto.

First, in step S1, the dye molecules and a co-adsorbent having at least one functional group selected from the group consisting of a diphenylphosphino group and a diphenyl ketone group are adsorbed on a porous layer containing oxide semiconductor particles formed on one surface of a transparent substrate The transparent substrate may be widely used within a range that secures transparency and heat resistance as well as a glass substrate such as a polymer substrate and the like, Conductive fine particles such as ITO, ZTO, and FTO are vapor-deposited to a thickness of several nanometers to several micrometers by a physical / chemical vapor deposition method such as sputtering and evaporation, and are usually used as transparent electrodes having electrical conductivity.

At least one oxide semiconductor particle selected from the group consisting of TiO ₂ , SnO ₂ , ZnO, WO ₃ , Nb ₂ O _5, and TiSrO ₃ is formed on the deposited conductive fine particle structure of the transparent substrate to have a thickness of from several to several tens of μm Layer. The porous layer means a porous layer which increases the interface between the dye molecules and the adsorbent to efficiently perform the photoelectric reaction.

Also, the dye molecules are not particularly limited as long as they are substances that can be transferred to the excited-base state by the sunlight, but the ruthenium dithiocyanate 2,2'-bipyridyl-4,4'- Dicarboxylate (ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate).

In addition, the co-adsorbent is a molecule having a dipole moment. Specifically, the co-adsorbent is composed of 2-hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone, 2- (Diphenylphosphino) ethyl-dimethylethoxy silane and 2- (Diphenylphosphino) ethyltriethoxy silane May be used.

Meanwhile, the method of manufacturing a dye-sensitized solar cell having a co-adsorbent according to the present invention may further include a step S11 of adding an adsorbing compound to the dye molecules and the co-adsorbent in step S1.

The co-adsorbent is used to prevent the dye molecules and the co-adsorbent from interfering with each other or adsorbed on the porous layer, or may be removed through a subsequent drying or heat treatment process.

These inclusion compounds include at least one selected from the group consisting of deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, polyethylene oxide, cholic acid, crown ether, cyclodextrin, calixarene or polyethylene oxide Can be used.

Next, in step S2, a counter electrode made of a metal material is formed on a substrate having a conductive oxide layer made of oxide semiconductor particles. The substrate can be made of glass or a polymer material, and the conductive The oxide layer refers to a layer formed by depositing oxide semiconductor fine particles such as ITO, ZTO, and FTO to a thickness of several nm to several 탆 by a physical / chemical vapor deposition method such as sputtering and evaporation.

The counter electrode is an electrode that opposes the photoelectrode and constitutes an electrical closed circuit, and may be mainly composed of a metal material.

Such a counter electrode is a structure in which the counter electrode is laminated on the conductive oxide layer of the substrate. The counter electrode is not particularly limited as long as it is a conductive material, and further includes a layer having a conductive material on the surface facing the photo electrode, For example, platinum, gold, and carbon can be seen. Platinum is in the state of platinum black, and carbon is in a porous state. The platinum black state is anodic oxidation, chloroplatinic acid treatment , And the porous state can be formed by a method such as sintering of carbon fine particles or firing of organic polymers.

Next, in step S3, the dye-sensitized solar cell module is prepared in which the photoelectrode and the counter electrode are spaced apart from each other, and an electrolyte is injected and sealed.

The photoelectrode and the counter electrode are disposed opposite to each other, a space for injecting an electrolyte therein is secured, the peripheral portion is fixed with an adhesive polymer resin, dried and sealed, Or an electrolyte solution is injected into the space between the two electrodes through the hole and then the hole is closed with an adhesive to form a dye sensitizing dye having a conjugate according to the present invention, A solar cell module can be manufactured.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments. It will be apparent to those skilled in the art that numerous modifications and variations can be made in the present invention without departing from the spirit or scope of the appended claims. And equivalents should also be considered to be within the scope of the present invention.

Example 1

(1) A transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed was prepared. The coating composition paste containing titanium dioxide was coated on the transparent conductive oxide layer of the substrate by a doctor blade method and heat-treated at 500 ° C for 30 minutes to contact and fill the nano- Nm thick nano-oxide layer. Then, a coating composition paste containing titanium dioxide was coated on the nano-oxide layer in the same manner and heat-treated at 500 ° C for 30 minutes to form a nioxide layer having a total thickness of about 15 μm. Then, a dye solution in which 0.3 mM of ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate and 0.3 mM of 2- (diphenylphosphino) ethyl-dimethylethoxy silane were dissolved in ethanol was prepared , And a glass substrate on which the nano-oxide layer was formed was carried thereon for 24 hours and dried to prepare a photoelectrode as a negative 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 hexachloroplatinic acid (H ₂ PtCl ₆ ) was dissolved was dropped on the transparent conductive oxide layer of the substrate, and then heat treatment was performed at 450 ° C. for 30 minutes to form a platinum layer, .

(3) After the nano-oxide layer of the photo electrode and the platinum layer of the counter electrode were opposed to each other, a thermoplastic polymer layer having a thickness of about 60 탆 and made of SURLYN (manufactured by Du Pont) (oven) and maintained at 130 ° C for 2 minutes to attach / seal the two electrodes. Next, a fine hole passing through the negative electrode and the positive electrode was formed, and 0.1 M LiI, 0.05 MI ₂ , 0.5 M 4-tert-butylpyridine and ion were added to the space between the two electrodes through a hole in the 3-Methoxypropionitrile solvent The electrolyte solution prepared by dissolving 0.6M 1-Ethyl-1-methylpyrrolidinium iodide, which is a liquid, was injected and then the outside of the hole was sealed with an adhesive.

Example 2

In the preparation of the dye solution, a dye solution in which 0.3 mM ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate and 0.3 mM 2- (Diphenylphosphino) ethyltriethoxy silane were dissolved was prepared The same procedure as in Example 1 was carried out.

Example 3

In the preparation of the dye solution, 0.3 mM ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate and 0.3 mM 2-Hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone Was prepared in the same manner as in Example 1, except that the dissolved dye solution was prepared.

Comparative Example

In the same manner as in Example 1 except that 0.2 mM ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate was dissolved in the preparation of the dye solution, Respectively.

Experimental Example

In order to evaluate the photoelectric conversion efficiency of the dye-sensitized solar cell prepared in Examples 1 to 3 and Comparative Examples, photoelectric characteristics were observed by measuring a photo voltage and photocurrent in the following manner, and the current density I _The photoelectric conversion efficiency (eta _e ) was calculated by the following equation (1) using the voltage ( _Vsc ), the voltage ( _Voc ) and the fill factor (ff).

At this time, a Xenon lamp (Oriel) was used as a light source, and the solar condition (AM 1.5) of the Xenon lamp was corrected using a standard solar cell.

&Quot; (1) "

Photoelectric conversion efficiency (? _E) = (V _oc x I _sc x ff) / (P _ine )

In Equation (1), (P _ine ) represents 100 mW / cm 2 (1 sun).

The measured values are shown in Table 1 below.

division Current density (mA / cm ² ) Voltage (V) Fill factor Photoelectric conversion efficiency (%) Example 1 15.706 0.774 0.662 8.058 Example 2 15.883 0.771 0.674 8.260 Example 3 16.033 0.738 0.648 7.679 Comparative Example 16.212 0.741 0.626 7.534

Referring to Table 1,

It was confirmed that the dye-sensitized solar cell having the co-adsorbent according to the present invention improved the photoelectric conversion efficiency as compared with the comparative example of the conventional dye-sensitized solar cell.

Claims (12)

delete A photoelectrode comprising a substrate on which a conductive film is stacked, a metal oxide layer coated on the electroconductive film, and a dye layer made of a mixture of a dye adsorbed on the metal oxide layer and a molecule having a dipole moment;
A counter electrode formed by sequentially depositing a conductive film and a platinum layer on the opposed surface of the second substrate on a surface opposite to the optical electrode;
A sealing member arranged and sealed along the rim of the photoelectrode and the counter electrode; And
And an electrolytic solution injected into a spaced space between the photoelectrode and the counter electrode,
Wherein the molecule has at least one functional group selected from the group consisting of a diphenylphosphino group and a diphenyl ketone group.
3. The method of claim 2,
Wherein the molecule is at least one selected from the group consisting of 2-Hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone, 2- (Diphenylphosphino) ethyl-dimethylethoxy silane and 2- (Diphenylphosphino) ethyltriethoxy silane. A dye-sensitized solar cell comprising the reinforced co-adsorbent.
3. The method of claim 2,
Wherein the dye is a ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate (2,2'-bipyridyl-4,4'-dicarboxylate) Dye - sensitized solar cell with enhanced co - adsorbent.
3. The method of claim 2,
Wherein the dye layer further comprises an inclusion compound. ≪ RTI ID = 0.0 > 11. < / RTI >
6. The method of claim 5,
Wherein the inclusion compound is at least one selected from the group consisting of deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, sodium cholate, polyethylene oxide, cholic acid, crown ether, cyclodextrin, calixarene or polyethylene oxide Wherein the dye-sensitized solar cell has a chemical bond-enhanced co-adsorbent.
delete A step S1 of forming a photoelectrode by adsorbing a dye and a co-adsorbent having a dipole moment on a porous layer containing fine oxide semiconductor particles formed on one surface of a substrate;
Forming a counter electrode made of a metal material on the second substrate having the conductive oxide layer made of oxide semiconductor particles; And
And preparing a dye-sensitized solar cell module in which the photoelectrode and the counter electrode are disposed so as to face each other and injected with an electrolyte to seal the dye-sensitized solar cell module,
Wherein the co-adsorbent is a compound having at least one functional group selected from the group consisting of a diphenyl phosphino group and a diphenyl ketone group.
9. The method of claim 8,
Wherein the co-adsorbent is at least one selected from the group consisting of 2-Hydroxy-4- (3-methyldiethoxysilyl-propoxy) -diphenylketone, 2- (Diphenylphosphino) ethyl-dimethylethoxy silane and 2- (Diphenylphosphino) ethyltriethoxy silane. A method for manufacturing a dye-sensitized solar cell having a bond-enhanced co-adsorbent.
9. The method of claim 8,
Wherein the dye is a ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate (2,2'-bipyridyl-4,4'-dicarboxylate) A method of manufacturing a dye-sensitized solar cell having an enhanced co-adsorbent. delete delete

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