KR20180029757A - Preparation method of a counter electrode for dye-sensitized solar cell, a counter electrode fabricated thereby and dye-sensitized solar cell comprising said counter electrode - Google Patents

Abstract

The present invention relates to a dye-sensitized solar cell counter electrode manufacturing method, a solar cell counter electrode manufactured by the method and a dye-sensitized solar cell including the counter electrode. More specifically, the dye-sensitized solar cell includes the counter electrode having an excellent catalyst feature, an excellent electrical feature and excellent bonding power to a substrate to obtain longtime stability and be manufactured at low temperatures so as to applicable to a flexible substrate like plastic and fiber. Graphene/PEDOT instead of a platinum catalyst, used in a dye-sensitized counter electrode, is manufactured by using electrostatic spray deposition in the counter electrode.

Description

TECHNICAL FIELD [0001] The present invention relates to a dye-sensitized solar cell, a dye-sensitized solar cell, and a dye-sensitized solar cell including the counter electrode and the counter electrode, -SENSITIZED SOLAR CELL COMPRISING SAID COUNTER ELECTRODE}

More particularly, the present invention relates to a method of manufacturing a dye-sensitized solar cell, comprising the steps of: i) preparing a dye-sensitized solar cell comprising i) graphene and a PEDOT: PSS compound In a solvent; Ii) spraying a solution of graphene and a PEDOT: PSS compound on a transparent substrate using Electrostatic Spray Deposition; Iii) drying the solvent at a temperature of 60 to 120 DEG C to form a graphene-PEDOT: PSS catalyst layer; (Iv) a step of immersing the catalyst layer in a sulfuric acid solution to remove the PSS, and a dye-sensitized solar cell including the counter electrode and the counter electrode manufactured by the method.

The dye-sensitized photovoltaic cell is represented by a photovoltaic solar cell disclosed by Gratzel et al., Switzerland in 1991. The dye-sensitized photovoltaic cell generally includes a photosensitive dye that absorbs visible light, a wide band gap energy , A counter electrode that is catalyzed, and an electrolyte filled therebetween. The dye-sensitized solar cell is advantageous in that its production cost is lower than that of a conventional silicon solar cell or a compound semiconductor solar cell, its efficiency is higher than that of an organic solar cell, and it is also environmentally friendly and transparent.

On the other hand, the counter electrode used in the dye-sensitized solar cell mainly uses platinum. The platinum catalyst required for the preparation of the counter electrode is currently being deposited by a sputtering method which requires a vacuum process. In the conventional counter electrode manufacturing method, a platinum compound is fired at a high temperature to produce platinum nanoparticles, or a carbon-based material (carbon, carbon nanotube, graphene) is placed on a TCO substrate in place of a platinum catalyst to produce a counter electrode have. However, in this method, expensive platinum catalysts should be used. If the carbon-based material is used alone, there is a problem that the adhesion to the substrate is deteriorated or the photoelectric efficiency of the solar cell is lower than that of platinum, and heat treatment at a high temperature is required.

Therefore, attempts have been made to manufacture counter electrodes with various composite materials. Korean Patent No. 1273567 discloses (a) a first substrate having high temperature resistance that does not deform at a temperature of 500 ° C or lower, a porous film comprising a carbon-based material and platinum nanoparticles, a pressure-sensitive adhesive layer and a second substrate A substrate; And (b) separating the first substrate having the high temperature resistance from the A substrate by a transfer method and moving the porous film and the adhesive layer to a second substrate, thereby forming a second substrate, an adhesive layer formed on the second substrate, Wherein the step of fabricating the A substrate comprises forming a porous film comprising a carbon-based material and platinum nanoparticles on one side of a first substrate having high temperature resistance, and A step of laminating a pressure-sensitive adhesive layer and a second substrate on a porous film containing the carbon-based material and platinum nanoparticles in order, and heat-pressing the substrate, wherein the porous film comprises a carbon-based material, a platinum nanoparticle, a binder and a solvent Is coated on one surface of a first substrate having high temperature resistance and heat-treated at a temperature of 450 to 500 ° C for 1 to 2 hours to form a dye-sensitized solar cell A method of manufacturing a counter electrode is disclosed. Also, Korean Patent No. 1541448 discloses a method for preparing a metal nanoparticle-conductive polymer composite material by mixing a conductive polymer aqueous solution and a metal precursor and then adding a reducing agent (Step 1); (Step 2) spin-coating the composite material of step 1 on a flexible substrate with a substrate coated with a transparent electrode; And a step (step 3) of heat treating the flexible substrate coated with the composite material of step 2 at a temperature of 100 to 200 ° C to form a counter electrode (step 3), wherein the metal nanoparticles are dispersed in the conductive polymer layer A method of manufacturing a counter electrode of a sensitive solar cell is disclosed. However, since the metal material used in the above literature also uses precious metals such as platinum and gold, the cost reduction is not significant, and the performance is also excellent.

On the other hand, Korean Patent No. 1406427 discloses preparing a first substrate; Forming an oxide semiconductor electrode on the first substrate; Adsorbing a dye on the oxide semiconductor electrode; Preparing a second substrate; Dispersing a conductive polymer in a first solvent to obtain a first solution; Dispersing a carbon material in a second solvent to obtain a second solution; Mixing the first solution and the second solution to obtain a composite solution in which the carbon material and the conductive polymer are dispersed; Applying the composite solution to the second substrate; Forming a conductive polymer-carbon composite electrode by heat-treating the composite solution at 100 to 150 ° C; And injecting an electrolyte between the first substrate and the second substrate after positioning the first substrate and the second substrate so as to oppose each other and then injecting an electrolyte into the space between the first substrate and the second substrate. The conductive polymer-carbon composite electrode disclosed in the above document can be highly appreciated in that it exhibits performance that is not inferior to a conventional platinum electrode without using a noble metal. However, in the case of PEDOT: PSS among the conductive polymers, There is a problem that the efficiency of the battery is deteriorated.

Korean Patent No. 1273567 Korean Patent No. 1541448 Korean Patent No. 1406427

Therefore, the technical problem to be solved by the present invention is to solve the problems of the prior art as described above, which can be manufactured at a low temperature with good long-term stability due to the excellent cost- The present invention provides a method of manufacturing a dye-sensitized solar cell relative electrode.

Another object of the present invention is to provide a dye-sensitized solar cell including the counter electrode and the counter electrode manufactured by the above method.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: i) dispersing a graphene and a PEDOT: PSS compound in a solvent; Ii) spraying a solution of graphene and a PEDOT: PSS compound on a transparent substrate using Electrostatic Spray Deposition; Iii) drying the solvent at a temperature of 60 to 120 DEG C to form a graphene-PEDOT: PSS catalyst layer; Iv) dipping the catalyst layer in a sulfuric acid solution to remove PSS.

The present invention also relates to a process for the preparation of the compound of formula I wherein the solvent is selected from the group consisting of isopropyl alcohol, ethanol, acetone, acetonitrile, tetrahydrofuran and methanol, And a solvent having a high BP is excluded), the present invention provides a method for manufacturing a dye-sensitized solar cell relative electrode.

In addition, in the present invention, the voltage applied to the substrate by the electrostatic spin deposition is 1 to 20 kV, the distance from the substrate is 1 to 100 cm, the solution injection rate is 1 to 500 μl / min The present invention also provides a method for manufacturing a dye-sensitized solar cell relative electrode.

The transparent substrate may include a metal electrode, metal nitride, metal oxide, carbon compound, or conductive polymer having FTO (F-doped SnO ₂ : SnO ₂ : F), ITO and an average thickness of 1 to 1000 nm The present invention also provides a method for manufacturing a dye-sensitized solar cell relative electrode, wherein the dye-sensitized solar cell is a flexible substrate coated with a conductive film.

In addition, the present invention provides a dye-sensitized solar cell counter electrode manufactured by the above method.

The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized solar cell counter electrode.

According to the present invention, a counter electrode prepared by electrostatic sputter deposition in place of the platinum catalyst used in the dye-sensitized counter electrode is a high-cost platinum catalyst used in the past It can be applied to flexible substrates such as plastics and fiber substrates because it has excellent catalytic properties and electrical characteristics, has excellent long-term stability due to its excellent adhesion with substrates, and can be manufactured at low temperatures. The process can be easily fabricated on a large area using a simple electrodeposition electrodeposition method.

1 is a schematic view of a process for explaining a method of manufacturing a counter electrode according to the present invention.
2 is a schematic view of a dye-sensitized solar cell including the counter electrode according to the present invention.
Fig. 3 is a photograph of a test sample of Comparative Example 1 and Example 1 using a tape in order to examine the adhesion to a substrate.
4 is a graph comparing current-voltage curves of the dye-sensitized solar cell according to Example 1 and Comparative Example 1 of the present invention.
FIG. 5 is a graph showing changes in crystal arrangement (a before sulfuric acid treatment and after sulfuric acid treatment) after removal of PSS by sulfuric acid treatment after graphene-PEDOT: PSS coating on a transparent substrate. Fig.
FIG. 6 is a graph showing the difference in electric conductivity after removal of PSS by performing graphene-PEDOT: PSS coating on the transparent substrate and sulfuric acid treatment before the sulfuric acid treatment

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the drawings attached hereto.

It will be understood by those skilled in the art that the following embodiments are merely illustrative of the present invention and that various changes may be made without departing from the spirit and scope of the present invention. It can be deformed. Wherever possible, the same or similar parts are denoted using the same reference numerals in the drawings.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Means that a particular feature, region, integer, step, operation, element and / or component is specified and that the presence or absence of other features, regions, integers, steps, operations, elements, and / It does not exclude addition.

The term "nano," as used herein, refers to a nanoscale ranging from 1 to 1,000 nm, and may optionally include microunits. In addition, the term "nanoparticles" described in the specification includes all types of particles having nanoscale.

The method for preparing a dye-sensitized solar cell counter electrode according to the present invention comprises the steps of: i) dispersing graphene and a PEDOT: PSS compound in a solvent; Ii) spraying a solution of graphene and a PEDOT: PSS compound on a transparent substrate using Electrostatic Spray Deposition; Iii) drying the solvent at a temperature of 60 to 120 DEG C to form a graphene-PEDOT: PSS catalyst layer; Iv) dipping the catalyst layer in a sulfuric acid solution to remove PSS.

In the method for producing a counter electrode according to the present invention, the step of dispersing i) graphene and a PEDOT: PSS compound in a solvent is not particularly limited, and a known dispersion method, for example, a method disclosed in Korean Patent No. 1406427 Lt; / RTI > However, in the present invention, the solvent may be selected from the group consisting of isopropyl alcohol, ethanol, acetone, acetonitrile, tetrahydrofuran (THF), and methanol It is preferable to dry at a relatively low temperature in order to prevent the substrate from being damaged when using a flexible substrate made of a plastic material.

The method for preparing a dye-sensitized solar cell relative electrode according to the present invention includes the step of spraying a solution in which graphene and a PEDOT: PSS compound are dispersed onto a transparent substrate using Electrostatic Spray Deposition. The electrodeposition electrodeposition method is one of the coating methods of solution, and is advantageous for automation and enlargement of the manufacturing process, and can be applied to various substrates without being restricted by the temperature of the substrate because the process temperature is low. In addition, in the case of the present invention, since the solvent having a low boiling point is used, the cost can be reduced by simplifying the mass production process. In addition, the thickness of the graphene compound deposited on the transparent electrode is 0.2 to 0.8 μm, and the amount and thickness of the graphene compound can be reduced by simplifying the mass production process. In the present invention, the conditions of the electrostatic sputter deposition are not particularly limited and can be appropriately adjusted according to the thickness of the catalyst layer formed on the substrate. A typical condition is that the voltage applied to the substrate is 1 to 20 kV, the distance from the substrate is 1 to 100 cm, and the solution injection rate is 1 to 500 μl / min.

A transparent conductive electrode (TCO) may be used as the conductive transparent substrate for the counter electrode 120 according to the present invention. For example, SnO ₂ : F or ITO may be used. But are not limited to, ordinary conductive films well known in the art. Also, the conductive electrode may be at least one selected from the group consisting of FTO (F-doped SnO ₂ : SnO ₂ : F), ITO or metal electrode having an average thickness of 1 to 1000 nm, metal nitride, metal oxide, carbon compound, and conductive polymer A conductive film may be coated. Therefore, as shown in FIG. 2, the counter electrode 120 may include a substrate 101, a conductive film 102 formed on the substrate, and a catalyst layer 121. In addition, since the above method can be performed at a low temperature, the substrate 101 to be used is not only applicable to a commonly used glass substrate, but also applicable to a flexible substrate such as plastic and fiber which should be used in a low temperature environment.

(Iii) drying the solvent at a temperature of 60 to 120 DEG C to form a graphene-PEDOT: PSS catalyst layer. According to an electrostatic spray deposition method on a conductive transparent substrate, To form a graphene / PEDOT: PSS layer, followed by a drying step. The drying is not particularly limited and can be appropriately adjusted depending on the type of the solvent used. However, considering the case where the material of the transparent substrate is flexible, that is, a plastic substrate, the drying temperature is preferably in the range of 60 to 120 ° C, and the type of the solvent is also selected in consideration of the drying temperature.

The method for preparing a dye-sensitized solar cell relative electrode according to the present invention comprises: iv) dipping the catalyst layer in a sulfuric acid solution to remove PSS. Generally, in PEDOT: PSS, the part showing electrical characteristics such as conductivity is the PEDOT part. However, since PEDOT has low solubility in solvents, PEDOT: PSS structure is prepared by adding PSS to PEDOT in order to increase the solubility in solvents and improve the utilization. However, when PSS is added, the solubility of the solvent is increased to increase the utilization, but the electrical characteristic is lower than that of the single PEDOT. (PEDOT: 300 to 50 S cm -1, PEDOT: PSS: <1 S cm -1) Therefore, in the present invention, the crystal structure of the catalyst layer is changed by removing PSS using sulfuric acid in the graphene / PEDOT: PSS structure The electric conductivity can be improved by 5 times or more. The sulfuric acid treatment can be performed by immersing in a dilute sulfuric acid solution for 0.5 to 5 minutes.

The dye-sensitized solar cell having the structure as shown in FIG. 2 can be manufactured by applying the dye-sensitized solar cell counter electrode as described above. The photoelectrode material used in the present invention is used in the form of a paste. Since the paste can be produced by a method well known in the art, the method is not particularly limited and will not be described in detail herein.

2, the electrolyte 130 is actually filled in the space between the photoelectrode 110 and the counter electrode 120. However, in practice, the metal oxide 130, which is the porous film 103 on which the dye is adsorbed, And can be uniformly dispersed in the inside of the nanoparticle layer. The electrolyte includes an oxidation-reduction derivative that receives electrons from the counter electrode by oxidation-reduction and transfers the dye to the dye of the photoelectrode, and is not particularly limited as long as it can be used in a conventional dye-sensitized solar cell. Specifically redox derivative is iodine (I) system, a bromine (Br) based, cobalt (Co) based, thiocyanate (SCN ^-) type, selenide cyan (SeCN ^-) from the group consisting of an electrolyte containing system 1 It is preferable that more than two species are selected. The electrolyte may also contain one or more polymers selected from the group consisting of polyvinylidene fluoride-co-polyhexafluoropropylene, polyacrylonitrile, polyethylene oxide and polyalkyl acrylate. Further, the electrolyte may be a polymer gel electrolyte containing one or more inorganic particles.

The solar cell may further include a thermally fusible polymer film or an adhesive that is a paste for sealing the semiconductor electrode and the counter electrode. The adhesive used herein may be a conventional material, and the kind thereof is not particularly limited .

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are provided for illustrative purposes only, and the scope of the present invention is not limited thereto.

[Example 1]

(Fabrication of photoelectrode)

Fluorine doped tin oxide glass (8 Ω / Sq., Pilkington, USA) was used as a transparent conductive substrate for the photoelectrode. (1) Mucasol (Sigma-Aldrich), (2) organic solvent washing, and (3) UV-03 surface treatment to remove organic substances in FTO glass. The area of the solar cell was 0.16 cm ₂ on the cleaned FTO glass using a doctor blade method and coated with commercially available TiO ₂ paste (Dyesol, 18NR-T), dried at 120 ° C. using an electric furnace, Lt; 0 &gt; C for 5 minutes, 450 [deg.] C for 15 minutes, and 500 [deg.] C for 15 minutes. TiO2 paste having a size of 400 nm (CCIC, PST-400C) was coated on a TiO ₂ film having a thickness of 6 μm and dried at 120 ° C. for 5 minutes at 350 ° C., 5 minutes at 375 ° C., For 15 minutes to prepare a 4 ㎛ scattering layer. A 10 μm thick TiO2 film was prepared by dissolving Y123 dye (0.1 mM THF / ethanol (v / v, 1/2) solution, Dyenamo, Sweden) and chenodeoxycholic acid (CDCA) (5 mM, Sigma-Aldrich) . And the dye was adsorbed on the electrode film for about 12 hours so that the dye was sufficiently adsorbed thereon to prepare a photoelectrode

(Preparation of counter electrode)

The same FTO glass that was used to make the photoelectrode to make the counter electrode was used. Two holes were drilled in the FTO glass using a drill. The perforated glass was ultrasonically washed with ethanol solution and then dried with nitrogen gas. After drying, the entire surface of the FTO glass was mixed with PEDOT: PSS and ethanol in a volume ratio of 1: 3, followed by ultrasonic treatment for 30 minutes. Thereafter, graphene (1 wt%) was mixed and a counter electrode was formed on the FTO substrate by electrostatic spray deposition. At this time, the voltage applied by the power supply (ESN-HV30) is ~ 9 kV and the distance from the FTO substrate is 3.5 cm. The solution was injected at a rate of 50 l / min using a syringe pump (KD Scientific, KDS220). After that, it was dried at about 80 ° C for 30 minutes. The prepared graphene / PEDOT: PSS counter electrode was immersed in a 0.1 M solution of sulfuric acid solution for about 1-2 minutes to remove the PSS and rinsed with distilled water to prepare a counter electrode.

(Electrolyte injection and sealing)

In the space between the above-prepared photo-electrode and the counter electrode 0.22 M [Co (II) - (bpy) 3] (B (CN) 4) 2, 0.05 M [Co (III) (bpy) 3] (B (CN ) ₄ ) ₃ , 0.1 M LiClO ₄ , and 0.8 M tBP, and then sealed with a conventional polymer resin to prepare a dye-sensitized solar cell having the structure of FIG.

[Comparative Example 1]

(Fabrication of photoelectrode)

Fluorine doped tin oxide glass (8 Ω / Sq., Pilkington, USA) was used as a transparent conductive substrate for the photoelectrode. (1) Mucasol (Sigma-Aldrich), (2) organic solvent washing, and (3) UV-03 surface treatment to remove organic substances in FTO glass. The area of the solar cell was 0.16 cm ₂ on the cleaned FTO glass using a doctor blade method and coated with commercially available TiO ₂ paste (Dyesol, 18NR-T), dried at 120 ° C. using an electric furnace, Lt; 0 &gt; C for 5 minutes, 450 [deg.] C for 15 minutes, and 500 [deg.] C for 15 minutes. TiO2 paste having a size of 400 nm (CCIC, PST-400C) was coated on a TiO ₂ film having a thickness of 6 μm and dried at 120 ° C. for 5 minutes at 350 ° C., 5 minutes at 375 ° C., For 15 minutes to prepare a 4 ㎛ scattering layer. A 10 μm thick TiO ₂ film was prepared by dissolving Y123 dye (0.1 mM THF / ethanol (v / v, 1/2) solution, Dyenamo, Sweden) and chenodeoxycholic acid (CDCA) (5 mM, Sigma-Aldrich) Solution. And the dye was adsorbed on the electrode film for about 12 hours so that the dye was sufficiently adsorbed thereon to prepare a photoelectrode

(Preparation of counter electrode)

The same FTO glass that was used to make the photoelectrode to make the counter electrode was used. Two holes were drilled in the FTO glass using a drill. The perforated glass was ultrasonically washed with ethanol solution and then dried with nitrogen gas. After drying, a Pt solution (5 mM ethanolic solution of chloroplatinic acid hexahydrate (H2PtCl6 6H2O)) was dropped on the entire surface of the FTO glass and sintered in an electric furnace at 400 ° C for 20 minutes to prepare a Pt counter electrode.

(Electrolyte injection and sealing)

In the space between the above-prepared photo-electrode and the counter electrode 0.22 M [Co (II) - (bpy) 3] (B (CN) 4) 2, 0.05 M [Co (III) (bpy) 3] (B (CN ) ₄ ) ₃ , 0.1 M LiClO ₄ , and 0.8 M tBP, and then sealed with a conventional polymer resin to prepare a dye-sensitized solar cell having the structure of FIG.

[Experimental Example 1]

The open-circuit voltage, the photocurrent density, the energy conversion efficiency and the fill factor of each dye-sensitized solar cell prepared in Example 1 and Comparative Example 1 were measured in the following manner, The results are shown in Table 1 below. Further, FIG. 4 shows a graph of current-voltage curves of the solar cells of Example 1 and Comparative Example 1 obtained under the condition of AM 1.5G 1 Sun.

(1) Open-circuit voltage (V) and photocurrent density (mA / cm 2)

: Open-circuit voltage and photocurrent density were measured using a Keithley SMU2400.

(2) Energy conversion efficiency (%) and fill factor (%)

: The energy conversion efficiency was measured using a solar simulator (Xe lamp [200 W, Polaronix ㄾ K201, McScience, Korea], AM1.5 filter) at 1.5 AM 100 mW / cm ² , Was calculated using the following formula.

[formula]

In the above equation, J is the Y-axis value of the conversion efficiency curve, V is the X-axis value of the conversion efficiency curve, and Jsc and Voc are the intercept values of the respective axes.

Jsc
(MA / cm ² ) Voc
(V) FF
(%) efficiency
(%) Area
(㎠) Example 1 13.64 0.92 67.01 8.33 0.16 Comparative Example 1 13.27 0.92 65.52 7.99 0.16

Fig. 3 is a photograph of a test sample of Comparative Example 1 and Example 1 using a tape in order to examine the adhesion to a substrate. As shown in FIG. 3, when the counter electrode was manufactured using only graphene, the adhesion of the graphene to the substrate was measured. As a result, almost all of the graphene peeled off was observed. However, the graphene / PEDOT: (Example 1), it can be seen that the adhesion to the substrate is excellent, and the catalyst layer remains at all. As shown in Table 1 and FIG. 4, in the case of the counter electrode (Example 1) made of graphene / PEDOT: PSS (Comparative Example 1), compared to the counter electrode (Comparative Example 1) , And the FF is high, thus confirming high efficiency.

FIG. 5 is a graph showing changes in crystal arrangement (a before sulfuric acid treatment and after sulfuric acid treatment) after removal of PSS by sulfuric acid treatment after graphene-PEDOT: PSS coating on a transparent substrate. And FIG. 6 is a graph showing a difference in electrical conductivity after removal of PSS by performing graphene-PEDOT: PSS coating on a transparent substrate and then sulfuric acid treatment before sulfuric acid treatment. As can be seen from FIGS. 5 and 6, not only the crystal arrangement of pores in the crystal arrangement after the sulfuric acid treatment, but also the electrical conductivity was about 4 times or more (23 s cm -1 before the sulfuric acid treatment, 105 s cm -1 after the sulfuric acid treatment ) I could see the difference. Therefore, the counter electrode made of the present invention is excellent in catalytic properties and electrical characteristics, has excellent long-term stability due to its excellent adhesion with the substrate, and can be manufactured at a low temperature, so that it can be applied to flexible substrates such as plastics and fibers, It can be used in applications where power is needed.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art will be able to modify the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the scope of the present invention as long as they are obvious to those skilled in the art.

101: transparent glass substrate
102: transparent conductive electrode
103: Porous film containing metal oxide nano-particles adsorbing dye
120: counter electrode
121: catalyst layer
130: electrolyte
140: polymer adhesive layer

Claims (7)

I) dispersing graphene and a PEDOT: PSS compound in a solvent;
Ii) spraying a solution of graphene and a PEDOT: PSS compound on a transparent substrate using Electrostatic Spray Deposition;
Iii) drying the solvent at a temperature of 60 to 120 DEG C to form a graphene-PEDOT: PSS catalyst layer;
Iv) dipping the catalyst layer in a sulfuric acid solution to remove PSS. The method according to claim 1,
The solvent may be at least one selected from the group consisting of isopropyl alcohol, ethanol, acetone, acetonitrile, tetrahydrofuran (THF), and methanol Type solar cell relative electrode manufacturing method. The method according to claim 1,
In the electrostatic spray deposition method, the voltage applied to the substrate is 1 to 20 kV, the distance from the substrate is 1 to 100 cm, and the solution is injected at a rate of 1 to 500 μl / min Wherein the dye-sensitized solar cell is a dye-sensitized solar cell. The method according to claim 1,
Wherein the catalyst layer coated on the transparent substrate has a thickness of 0.1 to 0.8 mu m after drying. The method according to claim 1,
The transparent substrate may include a conductive film comprising FTO (F-doped SnO ₂ : SnO ₂ : F), ITO and a metal electrode having an average thickness of 1 to 1000 nm, a metal nitride, a metal oxide, a carbon compound, Wherein the dye-sensitized solar cell is a flexible substrate. A dye-sensitized solar cell relative electrode produced by the method of any one of claims 1 to 5. A dye-sensitized solar cell comprising the dye-sensitized solar cell counter electrode of claim 6.

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