KR101409067B1 - Dye sensitized solar cell and its manufacturing method - Google Patents

Abstract

The present invention relates to a dye-sensitized solar cell and a method for manufacturing the same and, more specifically, to a dye-sensitized solar cell which satisfies the excellent energy conversion efficiency by increasing photoactivity and reducing the recombination rate of electrons by forming a coating layer capable of improving a light absorption capacity with low toxicity.

Description

[0001] The present invention relates to a dye-sensitized solar cell,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye-sensitized solar cell, and more particularly, to a dye-sensitized solar cell that improves photoactivity and decreases the recombination ratio of electrons, and a method for manufacturing the same.

The problem of depletion of resources is intensifying due to industrialization and industrialization which are getting more and more developed. The development of new and renewable energy to address this problem is a global concern, and the need for research on new energy sources and environmental technologies is emphasized. Therefore, instead of existing fossil fuel-based energy, the value standard for energy sources using clean nature such as sun, wind, and water is increasing.

A solar cell is an electricity generating device that directly converts sunlight into electricity by photovoltaic effect. Solar cells, which are already an important part of our lives, are simply used as power sources for clocks, calculators, etc., and are mainly used in aerospace fields such as satellite communications and large-scale electric power plants. The types of solar cells include silicon (Si) solar cells, inorganic solar cells, dye sensitized solar cells, organic solar cells, semiconductor pn junction type and semiconductor / liquid photochemical solar cells. Renewable energy sources.

The dye-sensitized solar cell is a solar cell that supplies electricity by using the principle of photosynthesis unlike a general semiconductor solar cell. It was originally designed by Gratzel in 1991. It is simple to manufacture, affordable, and widely used in everyday life. Accessibility is possible, which implies a lot of potential for future development.

In a dye-sensitized solar cell, when sunlight is incident on a solar cell, a photocatalyst is absorbed by a dye polymer adsorbed as a monolayer on the surface of the nanocrystal film, and thereby the dye polymer is excited. The excited dye molecules are oxidized by emitting electrons, and the emitted electrons move to the conduction band of the photocatalyst electrode. The electrons pass through the transparent electrode cell, transfer electric energy to the external load, and then move to the counter electrode. The platinum electrode, which is the most commonly used counter electrode, receives electrons from the electrolyte of the oxidation-reduction pair through the iodination reaction and returns to the original ground state.

The TiO ₂ photocatalyst most widely used as a photoelectrode for a dye-sensitized solar cell has the highest efficiency in a dye-sensitized solar cell, but has a problem that it has a very low efficiency as compared with other solar cells including a silicon solar cell .

In addition, various attempts have been made to improve the low efficiency of the dye-sensitized solar cell. However, the dye-sensitized solar cell has limitations in improving the photoelectric conversion efficiency and has toxicity and corrosiveness. Therefore, it is urgently required to develop a new technology for improving the efficiency.

Korean Patent Application Publication No. 1019980031527

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a dye-sensitized solar cell and a manufacturing method thereof.

In order to solve the above-mentioned problems, An electron mobility layer formed on one surface of the transparent electrode; A counter electrode arranged to face the electron mobility layer; And an electrolyte interposed in a space between the transparent electrode and the counter electrode, wherein the electron mobility layer comprises a porous film and a Zr coating film.

According to a preferred embodiment of the present invention, the porous film is made of TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ And Nb ₂ O ₅ , and the spherical structure may have an average diameter of 50 to 100 μm.

According to a preferred embodiment of the present invention, the average thickness of the porous membrane may be 20 to 30 탆.

According to a preferred embodiment of the present invention, the dye may include at least one selected from N3, N719, N749 and N886.

According to a preferred embodiment of the present invention, the Zr coating film may have a BET specific surface area value of 70 to 80 m ² / g, and the transparent electrode may include a substrate and a conductive material coating layer, A conductive material coating layer and a metal layer formed on the conductive material coating layer, and the substrate may be a transparent plastic substrate or a glass substrate including any one of PET, PEN, PC, PP, PI and TAC, The coating layer may include at least one of ITO, FTO, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O ₃ , and the metal layer may be at least one selected from the group consisting of Pt, Au, And may include at least one selected from Ru, Pd, Rh, Ir, Os, C, and Graphene. And the electrolyte is LiI, NaI, KI, 0.05 ~ 0.1MI 2 -, tetra-alkyl ammonium iodine (Tetra-alkyl ammonium iodide (R 4 NI)), 0.1 ~ 0.5M imidazolium derivative iodo disk (Imidazolium derivative iodedies ) And a nonprotonic solvent. The non-protonic solvent may be an iodine compound.

Another aspect of the present invention is to provide a dye-sensitized solar cell having a energy conversion efficiency (η) of 5.0 to 9.7% when calculated by the following formula (2) using a light source 1.5AM and a solar simulator having a light intensity of 100 mW / Thereby providing a battery.

&Quot; (2) "

[(V _oc x I _sc x FF) / (P _in x S)] x 100 (%)

(V _oc: voltage when current is not flowing (open-circuit voltage, V), I _sc: voltage current at the time 0 (danran current, mA), FF: a voltage theoretically the maximum voltage and the maximum current and the theoretical current P _in : intensity of irradiated light (100 mW / cm ² ), S: area of electrode (0.09 cm ² ))

According to another aspect of the present invention, there is provided a method of manufacturing a transparent electrode, comprising: (1) forming a porous film on one surface of a transparent electrode; (2) forming a Zr coating film on the porous film; (3) adsorbing a dye on the Zr coating film to form an electron mobility layer; (4) forming a counter electrode so as to face away from the electron mobility layer; And (5) injecting an electrolyte into a space between the transparent electrode and the counter electrode on which the electron mobility layer is formed.

According to another embodiment of the present invention, the step of forming the porous film comprises the steps of (1) mixing at least one porous powder selected from TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ and Nb ₂ O ₅ with 4 to 5 wt% 90 to 95% by weight of at least one solvent selected from water, ethanol, and methanol, and 0.5 to 1% by weight of at least one acid selected from nitric acid and acetic acid; (2) sonicating the mixed solution at 28 to 40 kHz; (3) After the ultrasonic treatment, 10 to 15 parts by weight of ethyl cellulose is added to 85 to 90 parts by weight of terpineol and 100 parts by weight of the mixed solution based on 100 parts by weight of the mixed solution, followed by stirring and drying to prepare a paste step; (4) applying the paste to the transparent electrode by any one selected from a spin coating method, a screen printing method, a spray coating method, a doctor blade method, and a squeeze method; And (5) baking at 350 to 500 ° C for 1 to 3 hours after the application.

According to another embodiment of the present invention, in the step of forming the Zr coating film, the transparent electrode having the porous film formed thereon may be immersed in a 40-50 mM zirconium precursor solution at 60-80 ° C for 20-60 minutes, and the zirconium nitrate Zirconium oxide, zirconium acetate, zirconium chloride, zirconium fluoride, zirconium hydroxide, zirconium oxide, and zirconium silicate And zirconium silicate. In the step of forming an electron mobility layer by adsorbing the dye, the transparent electrode transparent electrode having a Zr coating layer is coated with a dye solution at 15 to 25 ° C for 24 to 48 hours. Hour, and the dye solution is selected from the group consisting of N3, N719, N749 and N886 Choose books that can include any one or more.

According to another embodiment of the present invention, the counter electrode includes the steps of: (1) forming a conductive material coating layer on a substrate to form a transparent substrate; (2) punching at least one hole in the transparent substrate; (3) ultrasonically treating the transparent substrate with holes at 28 to 40 kHz for 10 to 20 minutes; (4) forming a metal layer on the ultrasonic treated transparent substrate; And (5) firing the transparent substrate having the metal layer formed thereon at a temperature of 250 to 400 ° C. for 40 to 80 minutes. The substrate may include any one of PET, PEN, PC, PP, PI and TAC A transparent plastic substrate or a glass substrate, and the conductive material coating layer may include at least one of ITO, FTO, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O ₃ , The metal layer is selected from platinum (Pt), gold (Au), ruthenium (Ru), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), carbon (C) and graphene And may include any one or more of them.

INDUSTRIAL APPLICABILITY The dye-sensitized solar cell of the present invention and the method of manufacturing the same provide a dye-sensitized solar cell and a method of manufacturing the dye-sensitized solar cell of the present invention by forming a coating layer having low toxicity and capable of improving light absorption capability, A sensitive solar cell can be provided.

1 is a cross-sectional view of a dye-sensitized solar cell according to a preferred embodiment of the present invention.
Fig. 2 is a graph of IV curves of Examples and Comparative Examples. Fig.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail with reference to the accompanying drawings.

As described above, the conventional dye-sensitized solar cell suffers from low photoelectric conversion efficiency. An electron mobility layer formed on one surface of the transparent electrode; A counter electrode arranged to face the electron mobility layer; And an electrolyte interposed in a space between the transparent electrode and the counter electrode, wherein the electron mobility layer includes a Zr coating layer on which a porous film and a dye are adsorbed, Respectively.

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

In the dye-sensitized solar cell 100, an electron mobility layer 20 is coated on one side of the transparent electrode 10, and the electron mobility layer 20 is coated with a Zr coating film 12 ). The counter electrode 50 is disposed so as to face the electrophoretic layer 20 so as to face the electrophoretic layer 20 and is fixed by the polymer film 40. The electrolyte 30 is disposed in the space between the transparent electrode 10 and the counter electrode 50 .

First, the transparent electrode 10 will be described.

The transparent electrode 10 of the present invention is excellent in thermal stability and has the advantages of low resistivity and high transmittance, and has a role of transmitting light and moving electrons to a conductive substrate. (PET), poly (ethylene terephthalate) (PEN), polycarbonate (PC), polypropylene (PP), and the like. The conductive transparent substrate of the dye-sensitized solar cell is not particularly limited as long as it is a conductive transparent substrate. ), polyimide (PI), and triacetyl cellulose (TAC) any of SnO _2, on a transparent substrate such as a transparent plastic substrate or a glass substrate comprising ITO (indium tin in the oxide), FTO (fluoine-doped tin oxide, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O ₃ (FTO) having high thermal stability, low surface resistance, and high light transmittance is most preferable.

Next, the electron mobility layer 20 formed on one surface of the transparent electrode 10 will be described.

The electron mobility layer 20 of the present invention may include a Zr coating layer 12 on which a porous film 11 and a dye 13 are adsorbed.

First, the porous film serves to move electrons and to transfer the adsorbed dye to the counter electrode and the electrolyte , And has an excellent conduction band energy value, a dye adsorption amount, excellent non-toxicity and chemical stability _{TiO 2, SnO 2, ZnO,} WO 3, TiSrO 3 And Nb ₂ O ₅ , and the spherical structure may have an average diameter of 50 to 100 nm. If the spherical structure has an average diameter of less than 50 nm, aggregation of the particles may occur, There may be a problem that migration is not smooth, and when it exceeds 100 nm, there is a problem that the surface area is large because the size is large.

The average thickness of the porous film may be 20 to 30 탆, and if the average thickness is less than 20 탆, the void may become too large and the dye adsorption may not be smoothly performed. If the average thickness exceeds 30 탆 , There may be a problem that the pores become too small and the electrons restrict the movement.

The following Zr coating film 12 can improve the photoactivity and decrease the recombination ratio of electrons by performing surface thin film treatment of zirconium (Zr) having excellent light absorbing ability and low toxicity on the porous film.

The dye 13 adsorbed on the Zr coating film serves to absorb sunlight to provide electrons, and is not particularly limited as long as it is a dye that adsorbs to a semiconductor layer of a dye-sensitized solar cell. More preferably, the dye 13 is a ruthenium complex; Xanthine-based pigments such as rhodamine B, rose bengal, eosin, and erythrosine; A cyanine dye such as quinoxian and cryptoxian; Basic dyes such as phenosapranin, capri blue, thiosine and methylene blue; Porphyrin compounds such as chlorophyll, zinc porphyrin and magnesium porphyrin; Other azo dyes; Phthalocyanine compounds; Anthraquinone type dye; And a polycyclic quinone-based pigment, and these may be used singly or in combination. In the present invention, most preferably, the dye includes N3 dye having red color and N719 dye, N749 dye having green color and N886 dye having black color, and may include any one or more selected from N3, N719, N749 and N886 have.

According to a preferred embodiment of the present invention, the Zr coating film may have a BET specific surface area value of 70 to 80 m ² / g and increase the amount of dye molecules adsorbed according to the BET specific surface area, Thereby increasing the amount of electrons generated from the dye.

The counter electrode 50 disposed so as to be spaced apart from the next electron mobility layer 20 may be disposed and fixed by the polymer membrane 40. In the present invention, the counter electrode 50 plays a role of activating a redox couple and is not particularly limited as long as it forms a dye-sensitized solar cell counter electrode. In the present invention, PET, PEN, PC , ITO, FTO, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O _{3 on} a transparent plastic substrate or glass substrate containing one of PP, PI and TAC (Au), ruthenium (Ru), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and cobalt (Co) on the conductive material coating layer. (C), and graphene (Graphene), and may include an electrochemically stable metal, carbon, a conductive polymer having no chemical reactivity with iodine contained in the electrolyte, and a metal layer containing at least one selected from the group consisting of Mixture and the like may be used.

And The polymer membrane 50 may include a thermoplastic polymer material that is cured by heat or ultraviolet rays, and more preferably, it may include an epoxy resin.

The electrolyte 30 interposed in the space between the transparent electrode 10 and the counter electrode 50 typically receives electrons from the counter electrode by oxidation and reduction in the dye sensitized solar cell and transmits the dye to the dye The electrolyte used in the present invention may be LiI, Nal, KI, 0.05 to 0.1 M < _{2 >} ^- , or an organic semiconductor material having a hole conduction function. At least one selected from the group consisting of Tetra-alkyl ammonium iodide (R ₄ NI), 0.1 to 0.5 M imidazolium derivative iodides and nonprotonic solvent, Based compounds may be preferred.

According to another aspect of the present invention, there is provided a dye-sensitized solar cell having a energy conversion efficiency (η) of 5.58 to 7.5% when calculated using a light source 1.5AM and a solar simulator with a light intensity of 100 mW / Provide solar cells. This has better conversion efficiency than conventional dye-sensitized solar cells (see Table 1). The solar simulator used here can consist of Xe lamp [300W, Oriel], AM1.5 filter and Keithley SMU2400.

&Quot; (2) "

[(V _oc x I _sc x FF) / (P _in x S)] x 100 (%)

(V _oc: voltage when current is not flowing (open-circuit voltage, V), I _sc: voltage current at the time 0 (danran current, mA), FF: a voltage theoretically the maximum voltage and the maximum current and the theoretical current P _in : intensity of irradiated light (100 mW / cm ² ), S: area of electrode (0.09 cm ² ))

According to another aspect of the present invention, there is provided a method of manufacturing a transparent electrode, comprising: (1) forming a porous film on one surface of a transparent electrode; (2) forming a Zr coating film on the porous film; (3) adsorbing a dye on the Zr coating film to form an electron mobility layer; (4) forming a counter electrode so as to face away from the electron mobility layer; And (5) injecting an electrolyte into a space between the transparent electrode and the counter electrode on which the electron mobility layer is formed.

First, the step of forming the porous film will be described.

In the present invention, a method of forming a porous film comprises the steps of: (1) forming a porous film using TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ And Nb ₂ O ₅ , 90 to 95 wt% of at least one solvent selected from water, ethanol and methanol, and 0.5 to 1 wt% of at least one acid selected from nitric acid or acetic acid, % By weight of the mixed solution; (2) sonicating the mixed solution at 28 to 48 kHz; (3) After the ultrasonic treatment, 85 to 90 parts by weight of terpineol and 10 to 15 parts by weight of ethyl cellulose are added to 100 parts by weight of the mixed solution, followed by stirring and drying to prepare a paste. (4) applying the paste to the transparent electrode by any one selected from a spin coating method, a screen printing method, a spray coating method, a doctor blade method, and a squeeze method; And (5) baking at 350 to 500 ° C for 1 to 3 hours after the application.

At this time, in the step of preparing the mixed solution, TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ And Nb ₂ O ₅ is less than 4% by weight, there may be a problem that other mixed solution may come out due to a small amount of TiO ₂ powder, and when it exceeds 5% by weight, the amount of the solution is excessively increased There may be a problem that aggregation of particles occurs. If less than 90% by weight of the solvent is selected from water, ethanol and methanol, the powder may not dissolve and aggregation may occur. When the amount of the solvent is more than 95% by weight, If the content of at least one acid selected from nitric acid or acetic acid is less than 0.5% by weight, there may be a coagulation phenomenon between the TiO ₂ particles. If the content exceeds 1% by weight, the particles may be scattered to reduce the area.

Ultrasonic treatment of 28 ~ 40KHZ can be performed 3 ~ 6 times in the following mixed solution, and TiO ₂ The particles can be evenly distributed without aggregation.

After ultrasonic treatment of the mixed solution, 85 to 90 parts by weight of terpineol may be added to 100 parts by weight of the mixed solution. If the mixing solution is less than 85 parts by weight, long-term stability may be unstable and the conductivity may be low If it exceeds 90 parts by weight, the transmittance may become too high. If 10 parts by weight of the mixed solution is added to 100 parts by weight of the mixed solution, if it is less than 10 parts by weight, there may be a problem that the viscosity of the mixed solution is insufficient, If it exceeds, there may be a problem that the particles aggregate due to high viscosity. After the addition of terpineol and ethylcellulose, the paste can be prepared by stirring and drying.

The paste prepared by the above method can be applied to the transparent electrode by any one method selected from spin coating, screen printing, spray coating, doctor blade and squeeze method. After the application, And then baked at 500 ° C for 1 to 3 hours to form a porous film. If the temperature is less than 350 ° C for firing and less than 1 hour, there may be a problem that bonding force between particles is insufficient. If the temperature exceeds 500 ° C and exceeds 3 hours, particles may be burned and disappear.

Next, in the step of forming the Zr coating film, the Zr coating film may be formed on one surface of the porous film by immersing the transparent electrode having the porous film formed thereon in a solution of 40 to 50 mM of zirconium precursor at 60 to 80 ° C for 20 to 60 minutes. The zirconium precursor solution may be at least one selected from the group consisting of zirconium nitrate oxide dihydrate, zirconium acetate, zirconium chloride, zirconium fluoride, zirconium hydroxide, One or more zirconium precursors selected from zirconium oxide and zirconium silicate. If the concentration of the zirconium precursor solution is less than 40 mM, there may be a problem that the Zr coating film is not appropriately formed and the dye adsorption amount is not increased. When the concentration is more than 50 mM, the Zr coating film is too thick, .

Next, in the step of adsorbing the dye to form an electron mobility layer, the porous film transparent electrode formed with the Zr coating film may be supported on the dye solution at a room temperature, preferably in a dye solution at 15 to 25 ° C for 24 to 48 hours The dye solution is not particularly limited as long as it plays a role of absorbing sunlight by adsorbing the dye solution on a semiconductor layer of a dye-sensitized solar cell to provide electrons, and more preferably a ruthenium complex; Xanthine-based pigments such as rhodamine B, rose bengal, eosin, and erythrosine; A cyanine dye such as quinoxian and cryptoxian; Basic dyes such as phenosapranin, capri blue, thiosine and methylene blue; Porphyrin compounds such as chlorophyll, zinc porphyrin and magnesium porphyrin; Other azo dyes; Phthalocyanine compounds; Anthraquinone type dye; And a polycyclic quinone-based pigment. These may be used singly or in combination, and most preferably, they may include any one or more selected from N3, N719, N749 and N886.

(1) forming a conductive material coating layer on the substrate to form a transparent substrate; and (2) forming a counter electrode on the counter electrode so as to face the counter electrode. (2) punching at least one hole in the transparent substrate; (3) ultrasonically treating the transparent substrate with holes at 28 to 40 kHz for 10 to 20 minutes; (4) forming a metal layer on the ultrasonic treated transparent substrate; And (5) firing the transparent substrate having the metal layer formed thereon at 250 to 400 ° C for 40 to 80 minutes. And wherein the substrate is PET, PEN, PC, PP, PI, and one may be a transparent plastic substrate or a glass substrate including said conductive material coating layer of the TAC is _{ITO, FTO, ZnO-Ga 2} O 3 ZnO-Al 2 O ₃ and SnO ₂ -Sb ₂ O ₃ , and the metal layer may include at least one of platinum (Pt), gold (Au), ruthenium (Ru), palladium (Pd), rhodium (Rh) Ir, osmium, carbon, and graphene.

In the present invention, when the counter electrode is formed, the transparent electrode having the hole is subjected to ultrasonic treatment to remove impurities from the transparent electrode, and the transparent electrode having the metal layer formed thereon is baked to serve as a catalyst capable of reducing the electrolyte .

The polymer membrane 50 may include a thermoplastic polymer material that is cured by heat or ultraviolet rays, and more preferably, it may include an epoxy resin.

The electrolyte may be injected into a space between the transparent electrode and the counter electrode through a hole formed in the next counter electrode. The electrolyte of the present invention typically receives electrons from the counter electrode by oxidation and reduction in a dye sensitized solar cell, But it is more preferable to use an ordinary iodine-based oxidizing and reducing electrolyte. A solution prepared by dissolving iodine in acetonitrile may be used.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

[ Example  One]

6 g of TiO ₂ powder (Degussa, P25) and 1 ml of acetic acid were placed in a mortar and mixed with distilled water and 130 ml of ethanol while mixing. The mixture was stirred and sonicated (28 to 40 kHz).

 Total ultrasonic treatment was performed 5 times. During the ultrasonic treatment, 20 g of terpinol and 3 g of ethyl cellulose were added and stirred, and ethanol was evaporated to prepare a paste.

Next, the FTO substrate was cut into a predetermined size (2 cm x 2.5 cm) and ultrasonically washed with ethanol and acetone for 15 minutes. After cleaning, the effective area of the electrode was set to 0.09 cm ^2, and the TiO ₂ paste was subjected to doctor blade To a thickness of 25 탆, followed by baking at 450 ^캜 for 2 hours.

After firing, 40 mM ZrO (NO ₃ ) ₂ 70 ^o C was applied to the cholesteric surface for 30 minutes. After completion of the surface thin film treatment, the electrode was immersed in dye N719. And left at room temperature for 24 hours or more so that the dye can be sufficiently adsorbed to the electrode while blocking the sunlight. In order to fabricate the counter electrode, two holes for injecting an electrolyte into the FTO substrate were sandblasted, and the hole-pierced electrodes were ultrasonicated for 15 minutes using ethanol and acetone, and then spin-coded -Coater) was used to uniformly apply a 10 mM platinum solution and fired at 350 ^° C for 1 hour to complete the counter electrode.

In order to assemble the transparent electrode on which the electron transporting layer was formed and the counter electrode, a surlyn paper as an adhesive was cut to a predetermined size, and the two electrodes were compressed and dried in an oven at 80 to 90 ° C. Thereafter, an iodine-based oxidation and reduction electrolyte (Solaronix, Iodolyte AN-50) was injected into the hole of the counter electrode, and the hole was sealed with 3M tape to prepare a dye-sensitized solar cell.

[ Example  2]

When the thickness of the porous film is Except that the thickness was 27 mu m.

[ Example  3]

Except that the Zr concentration was 45 mM.

[ Example  4]

Except that the Zr concentration was 50 mM.

[ Comparative Example  One]

Except that the Zr coating film was not formed.

[ Comparative Example  2]

Except that the thickness of the porous film was 7 占 퐉.

[ Comparative Example  3]

Of the porous membrane Except for the fact that the thickness was 66 占 퐉.

[ Comparative Example  4]

Except that the Zr concentration was 10 mM.

[ Comparative Example  5]

Except that the Zr concentration was 100 mM.

[ Comparative Example  6]

Except that the Zr concentration was 1000 mM.

[ Experimental Example  One]

The cells of Examples 1 to 4 and Comparative Examples 1 to 6 were irradiated with a light source 1.5 AM and a solar simulator (composed of Xe lamp (300 W, Oriel), AM 1.5 filter and Keithley SMU2400) with a light intensity of 100 mW / Energy conversion efficiency was measured.

The open-circuit voltage (Voc) and the photocurrent density (Jsc, mA / cm 2) were analyzed by using the IV curve of FIG. 2. The filling factor (FF:%) and the conversion efficiency And the results are shown in Table 1.

[Equation 1]

Filling factor (%) = ((J x V) _max / J _SC x V _OC ) x 100 where J is the Y axis value of the conversion efficiency curve, V is the X axis value of the conversion efficiency curve, and the photocurrent density (Jsc, mA / cm2) and Voc are the intercept values of the respective axes.

&Quot; (2) "

Conversion efficiency (侶:%) = [(V _oc x I _sc x FF) / (P _in x S)] x 100 (%).

(V _oc: voltage when current is not flowing (open-circuit voltage, V), I _sc: voltage current at the time 0 (danran current, mA), FF: a voltage theoretically the maximum voltage and the maximum current and the theoretical current P _in : intensity of irradiated light (100 mW / cm ² ), S: area of electrode (0.09 cm ² ))

Jsc (mA / cm ² ) Voc (V) FF (%) 侶 (%) Example 1 14.61 0.729 60.6 7.141 Example 2 16.90 0.761 60.1 9.742 Example 3 14.38 0.722 66.3 7.551 Example 4 14.90 0.726 66.2 7.873 Comparative Example 1 8.63 0.744 69.1 5.016 Comparative Example 2 10.96 0.734 63.6 5.884 Comparative Example 3 11.60 0.731 58.3 6.271 Comparative Example 4 12.133 0.716 60.6 5.897 Comparative Example 5 7.24 0.680 61.5 3.288 Comparative Example 6 1.46 0.749 59.6 0.712

As a result of the measurement, it can be seen that the efficiency of the example is higher than that of the comparative example. It can be seen that the Jsc value is increased by increasing the dye adsorption amount by forming a zirconium coating layer having low toxicity and high photoactivity. Also, since the coating layer is formed, the binding force of the particles is improved, and the electrons move smoothly, and the electron recombination ratio is reduced.

100: solar cell 10: transparent electrode 11: porous film
12: Zr coating film 13: dye 20: electron transfer layer
30: electrolyte 40: polymer membrane 50: counter electrode

Claims (14)

A transparent electrode;
An electron mobility layer formed on one surface of the transparent electrode;
A counter electrode formed to face the electron mobility layer; And
And an electrolyte interposed in a space between the transparent electrode and the counter electrode,
Wherein the electron mobility layer comprises a porous film and a Zr coating film having a BET specific surface area value of 70 to 80 m ² / g. The method according to claim 1,
The porous film may be formed of TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ And at least one spherical structure selected from Nb ₂ O ₅ ,
Wherein the spherical structure has an average diameter of 50 to 100 占 퐉. The method according to claim 1,
Wherein the average thickness of the porous film is 20 to 30 占 퐉. The method according to claim 1,
Wherein the dye is at least one selected from N3, N719, N749 and N886. delete The method according to claim 1,
Wherein the transparent electrode comprises a substrate and a conductive material coating layer,
Wherein the counter electrode comprises a substrate, a conductive material coating layer, and a metal layer. The method according to claim 6,
Wherein the substrate is a transparent plastic substrate or glass substrate comprising any one of PET, PEN, PC, PP, PI, and TAC,
Wherein the conductive material coating layer comprises at least one of ITO, FTO, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O ₃ ,
Wherein the metal layer is formed of at least one selected from platinum (Pt), gold (Au), ruthenium (Ru), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os) And a dye-sensitized solar cell. The method according to claim 1,
The electrolyte is LiI, Nal, KI, 0.05 ~ 0.1MI 2 -, tetra-alkyl ammonium iodine (Tetra-alkyl ammonium iodide (R 4 NI)), 0.1 ~ 0.5M imidazolium derivative iodo disk (Imidazolium derivative iodedies) And an iodine-based compound selected from the group consisting of a nonprotonic solvent and a nonprotonic solvent. Wherein the energy conversion efficiency (η) is 0.7 to 9.7% when calculated by the following formula (2) using a light source 1.5AM and a solar simulator having a light intensity of 100 mW / cm 2.
&Quot; (2) "
[(V _oc x I _sc x FF) / (P _in x S)] x 100 (%)
V _oc : voltage when no current flows (open-circuit voltage, V)
I _sc : current when the voltage is 0 (round current, mA)
FF: Maximum voltage and maximum current divided by theoretical voltage and theoretical current
P _in : intensity of irradiated light (100 mW / cm ² )
S: area of electrode (0.09 cm ² ) (1) forming a porous film on one surface of the transparent electrode;
(2) forming a Zr coating film on the porous film;
(3) adsorbing a dye on the Zr coating film to form an electron mobility layer;
(4) forming a counter electrode so as to face away from the electron mobility layer; And
(5) injecting an electrolyte into a space between the transparent electrode and the counter electrode on which the electron mobility layer is formed,
The Zr coating layer is formed by immersing a transparent electrode having a porous film on a 40 to 50 mM zirconium precursor solution at 60 to 80 ° C for 20 to 60 minutes to form a Zr coating film on one surface of the porous film,
The zirconium precursor solution may be selected from the group consisting of zirconium nitrate oxide dihydrate, zirconium acetate, zirconium chloride, zirconium fluoride, zirconium hydroxide, zirconium hydroxide, Wherein at least one zirconium precursor selected from the group consisting of zirconium oxide and zirconium silicate is included in the dye-sensitized solar cell. 11. The method of claim 10,
The step of forming the porous film
(1) 4 to 5% by weight of at least one porous powder selected from the group consisting of TiO ₂ , SnO ₂ , ZnO, WO ₃ , TiSrO ₃ and Nb ₂ O ₅ , 90 to 95% by weight of at least one solvent selected from water, By weight and 0.5 to 1% by weight of at least one acid selected from nitric acid and acetic acid;
(2) sonicating the mixed solution at 28 to 40 kHz;
(3) After the ultrasonic treatment, 10 to 15 parts by weight of ethyl cellulose is added to 85 to 90 parts by weight of terpineol and 100 parts by weight of the mixed solution based on 100 parts by weight of the mixed solution, followed by stirring and drying to prepare a paste step;
(4) applying the paste to the transparent electrode by any one selected from a spin coating method, a screen printing method, a spray coating method, a doctor blade method, and a squeeze method; And
(5) baking the coated substrate at 350 to 500 ° C for 1 to 3 hours after the application. delete 11. The method of claim 10,
The step of adsorbing the dye to form an electron mobility layer
Zr coating film is formed is supported on a dye solution at 15 to 25 ° C for 24 to 48 hours and dried,
Wherein the dye solution is at least one selected from N3, N719, N749, and N886. 11. The method of claim 10,
The counter electrode
(1) preparing a transparent substrate by forming a conductive material coating layer on a substrate;
(2) punching at least one hole in the transparent substrate;
(3) ultrasonically treating the transparent substrate with holes at 28 to 40 kHz for 10 to 20 minutes;
(4) forming a metal layer on the ultrasonic treated transparent substrate; And
(5) firing the transparent substrate on which the metal layer is formed at 250 to 400 ° C for 40 to 80 minutes,
Wherein the substrate is a transparent plastic substrate or glass substrate comprising any one of PET, PEN, PC, PP, PI, and TAC,
Wherein the conductive material coating layer comprises at least one of ITO, FTO, ZnO-Ga ₂ O ₃ ZnO-Al ₂ O ₃ and SnO ₂ -Sb ₂ O ₃ ,
The metal layer may be selected from among Pt, Au, Ru, Pd, Rh, Ir, Os, C, and Graphene. Wherein the dye-sensitized solar cell comprises at least one of the following materials:

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