KR101741941B1 - Synthesis of highly porous polyaniline/carbon nanodots nanocomposite and its application as counter electrodes in dye-sensitized solar cells - Google Patents

Abstract

The present invention relates to a method for producing a porous polyaniline / carbon nanotube nanocomposite using carbon nanotubes, which comprises preparing carbon nanotubes having a size of 1 to 15 nm and having a carboxyl group on the surface thereof, To provide a unique method of inhibiting the agglomeration of polyaniline and forming pores.
According to the present invention, it is possible to easily produce a polyaniline / carbon nanotube nanocomposite having a surface area increased by adding pores to a polyaniline polymerization solution by simply preparing the carbon nanotubes. The polyaniline / carbon nanoparticle nanocomposites with increased surface area due to the effect of carbon nano-dots have been shown to improve the interaction between the dopant camphorsulfonic acid and the methacresol solvent, and thus the polyaniline / carbon nanoparticle nanocomposite It is possible to manufacture a thin film. When the prepared polyaniline / carbon nano-dot nanocomposite thin film was used as a counter electrode of a dye-sensitized solar cell, the electrocatalytic activity was improved due to the improved electrical conductivity, and the electric power of the dye- An increase in power conversion efficiency can be expected.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous polyaniline / carbon nanotube nanocomposite and a dye-sensitized solar cell,

The present invention relates to a method for producing polyaniline / carbon having a pore size of about 20 to 50 nm by using carbon nanotubes (CNDs) as a nucleating agent in a polymerization process of a conductive polymer, polyaniline (PANI) The present invention relates to a method for producing a porous PANI / CND nanocomposite, which comprises doping a polyaniline / carbon nanotube nanocomposite having increased porosity and increased surface area and doping and solubilizing the same to form a conductive polymer thin film having high electrical conductivity . Furthermore, this method is applied to a counter electrode (CE) of a dye-sensitized solar cell (DSSC), and suggests a method of fabricating a dye-sensitized solar cell having high power conversion efficiency.

Conductive polymers that can be processed in solution have been attracting attention due to their advantages such as adjustable electrical properties, flexibility of electrodes, and excellent processability for easily fabricating thin films. As solution-processable conducting polymers, poly (3,4-ethylenedioxythiophene): polystyrene (PEDOT: PSS, poly (3,4-ethylenedioxythiophene) polyaniline / polystyrene sulfonate (PANI), polyaniline / polystyrene sulfonate (PANI / CSA), polyaniline / polystyrene sulfonate (PANI) . Among them, poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS), due to its excellent electrical properties with an electric conductivity of about 1000 S / cm and a hole transfer rate of about 20 cm ² / Vs And has been used as an electrode material for various electronic devices. Polyaniline / camphorsulfonic acid (PANI / CSA) has the highest electric conductivity of about 500 S / cm among the polyaniline-based conductive polymers, but poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) . However, compared to the price of 3,4-ethylenedioxythiophene, which is a monomer of poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) (12,000 won per gram), polyaniline / camphorsulfonic acid (PANI / CSA) as an electrode material for electronic devices due to the advantage that the price of aniline (PANI / CSA) monomer (4,300 won / g) is much cheaper (Sep. 15, Sigma Aldrich) Studies have been actively carried out to improve the electrical performance of the device.

One of the main factors that deteriorate the performance of polyaniline / camphorsulfonic acid (PANI / CSA) is the agglomeration of polymer in the polymerization process. In order to induce polymerization in the para-direction of polyaniline, the reaction proceeds at a low temperature of about -40 ^° C. Because of this, the reaction rate is slowed. Therefore, in order to obtain a polymer having 30 wt% The above polymerization reaction time is required. In the early stage of polymerization, polyaniline with pores of 20 to 50 nm, which is originally formed, is subjected to a secondary polymerization in which a newly formed polymer is adhered to the existing structure due to a long polymerization reaction time. As a result, polymerization reaction At the end, it is transformed into polyaniline with small surface area. Polyaniline, which has a smaller surface area due to the polymer aggregation phenomenon, has less interaction with a dopant or a solvent, resulting in a loss of electrical conductivity since the crystallinity of the produced thin film is lowered. Therefore, in order to use low-cost polyaniline as an electrode material for an electronic device, an effective method for improving the electrical conductivity of a thin film produced by maintaining a polyaniline structure having inherent porosity regardless of polymerization reaction time is strongly demanded.

It is an object of the present invention to provide a method for preparing a porous polyaniline / carbon nanotube nanocomposite having a wide surface area by using a method of introducing a carbon nanotube as a nucleating agent, The present invention relates to a conductive polymer thin film having improved electrical conductivity through secondary doping and solubilization.

An object of the present invention is to provide a method of manufacturing a dye-sensitized solar cell having a high power conversion efficiency by using the polyaniline / carbon nano-dot nanocomposite thin film produced by the above method as a counter electrode of a dye-sensitized solar cell have.

After many experiments and intensive studies, the inventors of the present invention have found that by completely producing carbon nanotubes and adding them as nucleating agents to polyaniline polymerization solutions, the porous structure of polyaniline is retained even after a long polymerization time The present inventors have found that a polyaniline / carbon nano-dot nanocomposite thin film having improved electrical conductivity and electrical catalyst activity as a counter electrode for a dye-sensitized solar cell can be produced.

In the present invention, carbon nanotubes are prepared by hydrothermal synthesis using citric acid as a precursor, amide bonding is performed by adding it to an aniline monomer solution, and then self-stabilized dispersion polymerization (SSDP) The polyaniline / carbon nanotube nanocomposite was prepared and dissolved in meta-cresol and chloroform solvent through secondary doping using camphorsulfonic acid. The polyaniline / carbon nanotube nanocomposite solution was then subjected to a solution process to form an FTO electrode A polyaniline / carbon nanotube nanocomposite thin film is prepared and finally applied as a counter electrode of a dye-sensitized solar cell.

The method for manufacturing a counter electrode thin film of a dye-sensitized solar cell using a porous polyaniline / carbon nanotube nanocomposite according to the present invention comprises:

(A) preparing a carbon nano-dot having an average diameter of 1 to 15 nm through a hydrothermal synthesis method and adding an amide bond to an aniline monomer solution by adding carbon nano dots;

(B) preparing a porous polyaniline / carbon nano-sized nanocomposite powder by self dispersion polymerization; And

(C) removing the dopant of the polyaniline / carbon nanotube nanocomposite powder in an emeraldine salt state by using an ammonia solution; And

(D) a second doping treatment of the doped polyaniline / carbon nanotube nanocomposite powder using camphorsulfonic acid; And

(E) preparing a polyaniline / carbon nano-sized nanocomposite solution for coating by dissolving the secondarily doped polyaniline / carbon nano-sized nanocomposite powder in a solution of meta-cresol and chloroform, followed by stirring and ultrasonic dispersion treatment; And

(F) drop-casting or spin-coating a polyaniline / carbon nano-dot nanocomposite solution to an appropriate thickness on an FTO electrode, and then forming a thin film for a dye-sensitized counter electrode;

(G) Assembling the dye-sensitized solar cell using the polyaniline / carbon nano-dot nanocomposite thin film as a counter electrode.

The method of inducing nucleation of the polyaniline polymerization process using the carbon nanotubes according to the present invention is an entirely new method which has not been reported so far and is a method in which carbon nanotubes prepared by a very simple method are added to a polymerization solution , It is possible to maintain a nanostructure having pores having a size of 20 to 50 nm, which is a form of initial polyaniline, even at a long polymerization time. It is possible to remarkably reduce the aggregation phenomenon between the polymers generated after polymer polymerization for 12 hours or more, which has been a problem in the previous method, and thus to improve the electrical conductivity of the polyaniline thin film after the polymerization process. In addition, with the improvement of the electrical properties, the added carbon nano dots induce continuous nucleation during the polymerization reaction, and thus the yield of polyaniline relative to the monomer can be greatly improved during the same polymerization time.

1 (a) is a photograph of a carbon nano-point powder prepared by a hydrothermal synthesis method, (b) is a transmission electron microscopy (TEM) photograph of a carbon nano-
2 (a) is a photograph of a polyaniline / carbon nano-dot nanocomposite powder obtained by a polymerization reaction, and (b), (c) and (d) are photographs of a polyaniline / carbon nano- SEM (scanning electron microscope) photograph of point nanocomposites,
3 shows the surface area and total pore volume of the polyaniline / carbon nanocomposite nanocomposite according to the weight ratio of the added carbon nano dots to that of the Brunauer-Emmett-Teller method using nitrogen adsorption / desorption (BET) ), Which is a table measured and compared,
4 is a graph showing the electrical conductivity of the polyaniline / carbon nano-dot nanocomposite thin film according to the weight ratio of the added carbon nano dots,
5 is a photograph of a counter electrode for a dye-sensitized solar cell in which a polyaniline / carbon nanotube nanocomposite thin film is spin-coated on an FTO electrode and a dye-sensitized solar cell assembled using the counter electrode,
6 (a) is a graph showing a current density (J) -voltage (V) of a solar cell including a polyaniline / carbon nanotube nanocomposite thin film counter electrode according to a weight ratio of carbon nanotubes added, Current density (J) - Voltage (V) of a photovoltaic cell including a counter electrode made by drop-casting and spin-coating a polyaniline / carbon nanotube nanocomposite thin film doped with 5 wt% ) Graph.

Unless otherwise specified herein, numerical ranges such as temperature, content, size and the like refer to ranges within which the manufacturing method of the present invention can be optimized.

In step (A), precursors containing carbon are placed in an autoclave at 180 ^° C for 4 hours to hydrothermally synthesize carbon nanotubes to be used as nucleating agents. Citric acid, glucose, chitosan and the like can be used as the precursor, but it is preferable to use citric acid in order to produce carbon nano dots having a carboxyl group on the surface. In the case of a method for producing carbon nano dots, hydrothermal synthesis is generally used, but pyrolysis of precursors using a microwave of a domestic microwave oven can also be used in the absence of an autoclave. The obtained carbon nano dots were added to a solution obtained by dissolving 2 g of aniline in 40 mL of 1 molar hydrochloric acid, and boric acid was added as a catalyst for the amide bond of carbon nano dots and aniline salt, followed by stirring at 50 ^° C for 3 hours Respectively. As the catalyst for the amide bond, it is preferable to use boric acid, which is an acid type catalyst, so as not to inhibit the aniline from being positively charged, and it is suitable to add only 1 mg of boric acid to be added.

In step (B), chloroform (chloroform) is added to the aniline monomer solution to which carbon nano dots are added at a volume ratio of 2: 3, and ammonium peroxide is added as an initiator to initiate polymerization. Oxidation polymerization with ammonium peroxide and production of polyaniline through oligomerization of low molecular weight oligomers and self-dispersion polymerization in which unreacted monomers act as a dispersant are preferable for obtaining a thin film having high electrical conductivity. The lower the polymerization temperature increases the lower the molecular weight, but known that conductivity is improved, and the polydispersity increases, the molecular weight control becomes difficult, -40 ^o C is the recommended degree. The amount of ammonium peroxide to be added as an oxidant for initiating the oxidation polymerization is preferably 2 to 2.4 g per 2 g of the aniline monomer. When the initiator is added thereto, an excess amount of the radical cationic monomer anilinium salt, And the electrical conductivity is reduced. When the stirring time in the polymerization step is short, the yield is low, and when the stirring time is long, polymer is entangled so that 12 to 16 hours is suitable.

In step (C), the polyaniline powder in an emeraldine salt state obtained after the completion of the polymerization reaction is dispersed in an ammonia solution and then subjected to a reduction reaction by stirring to remove the dopant to form a brown emeraldine base. To obtain a polyaniline powder. The amount of ammonia to be added is preferably about 0.5 to 1.0 mol per 1 L of water, and the reduction reaction time is preferably 12 hours or more, but is not limited to these ranges and may be more than the above range. The reducing agent used for doping removal is not particularly limited as long as it is a basic solution capable of reducing the hydrogen acid ion of polyaniline in an emeraldine salt state.

In step (D), camphorsulfonic acid is added to and mixed with the doped emeraldine base polyaniline powder to carry out secondary doping treatment. The amount of camphorsulfonic acid to be added is preferably 1.20 to 1.25 g per 1.0 g of the emeraldine base polyaniline in order to obtain a viscosity suitable for processing in dissolving in meta-cresol and chloroform solvents. In the case of the secondary dopant used, camphorsulfonic acid capable of strong hydrogen bonding with the meta-cresol molecule is most preferable, but organic acids having a high molecular weight such as dodecylbenzenesulfonic acid (DBSA) can also be used as a secondary dopant. As a method of doping polyaniline powder and camphor sulfonic acid, a method of finely grinding two powders using a mortar is suitable.

In step (E), a polyaniline / carbon nano-dot nanocomposite solution is prepared by stirring a polyaniline / carbon nano-point powder mixed with camphorsulfonic acid and meta-cresol and chloroform solvent, followed by sonication dispersion. The amount of the meta-cresol solvent is preferably in the range of 2.2 mL to 2.3 mL with respect to 0.1 g of the polyaniline / carbon nano-point powder, and the amount of the chloroform solvent is preferably in the range of 0.9 mL to 1.0 mL, which is preferable for producing a solution having an appropriate viscosity. The stirring and ultrasonic dispersion are alternately carried out and dispersed for more than 24 hours is suitable for dissolving all the powders.

In step (F), the polyaniline / carbon nanocomposite nanocomposite solution is prepared as a thin film for a counter electrode of a dye-sensitized solar cell using a solution process. A fluorine-doped tin oxide (FTO) glass electrode (15 Ohm / cm & lt ^; " ² > Drop-casting or spin-coating may be used as a solution processing method for applying the polyaniline-carbon nanotube nanocomposite solution on the FTO electrode. The polyaniline / carbon nanotube nanocomposite thin films with a thickness of 5 μm to 50 μm and a spin-coating thickness of 500 nm to 5 μm can be produced by drop-casting. The ideal sheet resistance of the dye-sensitized solar cell as a counter electrode is about 20 Ohm / cm < ² & gt ^;, so that a 650 nm thick polyaniline / carbon nano-dot obtained by a spin- Nanocomposite films are most suitable. Polyaniline / carbon nano nanocomposite material solution drop-after coating meta-casting or spin-cresol, and the temperature and time recommended for the vaporization of the chloroform solvent, but is recommended to heat the for about 10 hours at about 40 ^o C, the above But is not limited to the range.

In step (G), a working electrode of the dye-sensitized solar cell is prepared and bonded to the prepared polyaniline / carbon nano-dot nanocomposite thin film to complete the dye-sensitized solar cell. The FTO electrode is immersed in 0.04 mol of titanium tetrachloride per liter of water for 30 minutes, pre-treated, and heated at 450 ^° C for 30 minutes. Titanium dioxide nanoparticle pastes (Ti-nanoxide, Solaronix) are formed on the pretreated FTO electrodes by screen-printing to form 10 μm thick titanium dioxide nanoparticles. In order to adsorb the dye, an electrode formed with titanium dioxide nanoparticles described above is immersed in a 0.0005 molar concentration of N719 (Solaronix) dye solution to 1 L of ethanol. The recommended temperature and time for dye adsorption is about 18 ^o C at 25 ^o C, but is not limited to the above range. The fabricated working electrode and the counter electrode were sandwiched using a surlyn, and the dye sensitized solar cell was assembled by inserting an iodine redox electrolyte (I ^- / I ₃ ^- redox electrolyte) between the two electrodes do.

Hereinafter, specific examples of the present invention will be described with reference to examples, but the scope of the present invention is not limited thereto.

2 g of citric acid is placed in an autoclave and hydrothermally synthesized at 180 ^° C. for 4 hours to obtain an orange gel-type solution, which is neutralized with a 10 mg / ml sodium hydroxide solution. The neutralized solution is added with ethanol, centrifuged to remove the salt, and dried in an oven to obtain a carbon nano-point powder. It was confirmed through TEM (transmittance electron microscopy) that the size was about 4 nm and that the surface was rich in carboxyl groups through X-ray photoelectron spectroscopy (XPS).

2 g of citric acid is added to 20 mL of distilled water and stirred to completely dissolve it. Put it in a glass bottle and heat it for 3 minutes in a household microwave oven. (Output: 700 W) Cool it at room temperature and dissolve the red brown foamy solid in 50 mL of distilled water. Then add ethanol to remove the salt and centrifuge to dry the carbon nano powder. Can be obtained. It was confirmed by TEM (transmission electron microscopy) that the size was about 2.8 nm and that the surface was rich in carboxyl groups through X-ray photoelectron spectroscopy (XPS).

2 g of glucose is added to 20 mL of distilled water and stirred to completely dissolve it. Then, it is put in a glass bottle and heated in a domestic microwave oven for 4 minutes and 30 seconds. (Output: 700 W standard) After cooling at room temperature, the obtained brown solution is centrifuged with ethanol, and dried to obtain a carbon nano-point powder. It was confirmed by TEM (transmission electron microscopy) that the size was about 4.8 nm and that the surface was rich in carboxyl groups through X-ray photoelectron spectroscopy (XPS).

Add 2 g of aniline monomer to 40 mL of 1 molar hydrochloric acid, add 60 mL of chloroform, and lower the temperature to -40 ^° C with stirring to polymerize at low temperature. In this process, when the temperature reaches -10 ^° C, the polymerization reaction is started by injecting a initiator solution in which 2.4 g of ammonium peroxide is dissolved in 10 ml of 1 molar hydrochloric acid. 16 hours after the initiator solution is injected, the polyaniline powder can be obtained by centrifuging the polymerization solution. The surface area calculated by the Brunauer-Emmett-Teller (BET) method was 12.43 m ² / g and the total pore volume was 0.051 cm ³ / g.

The obtained polyaniline powder was dispersed in 200 mL of a 1-molar ammonia solution and stirred for 24 hours to reduce it.

The reduced polyaniline powder is obtained by centrifugation, and 1.2 g of camphor sulfonic acid is mixed per 1 g of the polyaniline powder to perform second doping treatment. By mixing 0.165 g of the second-doped polyaniline powder in 3.5 mL of meta-cresol and 1.5 mL of chloroform, stirring and ultrasonic dispersion treatment for 12 hours or more can be carried out to obtain a viscous polyaniline solution.

The solution is applied to produce a polyaniline thin film having an electrical conductivity of about 596 S / cm.

2 g of aniline monomer and 1 wt% of an aniline monomer and 1 mg of boric acid are added to 40 mL of 1 molar hydrochloric acid, and the mixture is stirred at 50 ^° C for 3 hours to form an amide bond.

After the carbon nano dots and the aniline monomer are amide bonded, add 60 mL of chloroform and lower the temperature to -40 ^° C while stirring to polymerize at a low temperature. In this process, when the temperature reaches -10 ^° C, the polymerization reaction is started by injecting a initiator solution in which 2.4 g of ammonium peroxide is dissolved in 10 ml of 1 molar hydrochloric acid. After 16 hours from the injection of the initiator solution, the polyaniline / carbon nanocomposite nanocomposite powder can be obtained by centrifuging the polymerization solution. The surface area calculated by the Brunauer-Emmett-Teller (BET) method was 18.79 m ² / g and the total pore volume was 0.096 cm ³ / g.

The obtained polyaniline / carbon nano-sized nanocomposite powder was dispersed in 200 mL of 1 molar ammonia solution and stirred for 24 hours for reduction.

The polyaniline / carbon nano-sized nanocomposite powder reduced by centrifugation is obtained, and 1.2 g of camphor sulfonic acid is mixed per 1 g of the polyaniline / carbon nano-dot nanocomposite powder to perform second doping treatment. When dispersing 0.165 g of the polyaniline / carbon nano-dot nanocomposite powder subjected to the second doping treatment in a mixture of 3.5 mL of meta-cresol and 1.5 mL of chloroform, stirring and ultrasonic dispersion treatment for 12 hours or more were carried out to obtain a viscous polyaniline / A composite solution can be obtained.

The polyaniline / carbon nanotube nanocomposite thin film having an electrical conductivity of about 610 S / cm can be prepared by applying the solution.

2 g of aniline monomer and 5 wt% of an aniline monomer and 1 mg of boric acid are added to 40 mL of 1 molar hydrochloric acid, followed by stirring at 50 ^° C for 3 hours.

After the carbon nano dots and the aniline monomer are amide bonded, add 60 mL of chloroform and lower the temperature to -40 ^° C while stirring to polymerize at a low temperature. In this process, when the temperature reaches -10 ^° C, the polymerization reaction is started by injecting a initiator solution in which 2.4 g of ammonium peroxide is dissolved in 10 ml of 1 molar hydrochloric acid. After 16 hours from the injection of the initiator solution, the polymer solution is centrifuged to obtain a polyaniline / carbon nanotube nanocomposite powder. The surface area calculated by the Brunauer-Emmett-Teller (BET) method was 43.64 m ² / g and the total pore volume was 0.255 cm ³ / g.

The resulting polyaniline / carbon nano-sized nanocomposite powder was dispersed in 200 mL of a 1-molar ammonia solution and stirred for 24 hours to reduce it.

The polyaniline / carbon nano-sized nanocomposite powder reduced by centrifugation is obtained, and 1.2 g of camphor sulfonic acid is mixed per 1 g of the polyaniline / carbon nano-dot nanocomposite powder to perform second doping treatment. When dispersing 0.165 g of the polyaniline / carbon nano-dot nanocomposite powder subjected to the second doping treatment in a mixture of 3.5 mL of meta-cresol and 1.5 mL of chloroform, stirring and ultrasonic dispersion treatment for 12 hours or more were carried out to obtain a viscous polyaniline / A composite solution can be obtained.

The solution is applied to produce a polyaniline / carbon nanotube nanocomposite thin film having an electrical conductivity of about 774 S / cm.

2 g of aniline monomer, 40 wt% of aniline monomer, and 1 mg of boric acid are added to 40 mL of 1 molar hydrochloric acid, and the mixture is stirred at 50 ^° C for 3 hours.

After the carbon nano dots and the aniline monomer are amide bonded, add 60 mL of chloroform and lower the temperature to -40 ^° C while stirring to polymerize at a low temperature. In this process, when the temperature reaches -10 ^° C, the polymerization reaction is started by injecting a initiator solution in which 2.4 g of ammonium peroxide is dissolved in 10 ml of 1 molar hydrochloric acid. After 16 hours from the injection of the initiator solution, the polymer solution is centrifuged to obtain a polyaniline / carbon nanotube nanocomposite powder. The surface area calculated by the Brunauer-Emmett-Teller (BET) method was 34.04 m ² / g and the total pore volume was 0.184 cm ³ / g.

The resulting polyaniline / carbon nano-sized nanocomposite powder was dispersed in 200 mL of a 1-molar ammonia solution and stirred for 24 hours to reduce it.

The polyaniline / carbon nano-sized nanocomposite powder reduced by centrifugation is obtained, and 1.2 g of camphor sulfonic acid is mixed per 1 g of the polyaniline / carbon nano-dot nanocomposite powder to perform second doping treatment. When dispersing 0.165 g of the polyaniline / carbon nano-dot nanocomposite powder subjected to the second doping treatment in a mixture of 3.5 mL of meta-cresol and 1.5 mL of chloroform, stirring and ultrasonic dispersion treatment for 12 hours or more were carried out to obtain a viscous polyaniline / A composite solution can be obtained.

The solution is applied to produce a polyaniline / carbon nanotube nanocomposite thin film having an electrical conductivity of about 748 S / cm.

The polyaniline / carbon nanoparticle nanocomposite prepared by adding 1 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dissolved in meta-cresol and chloroform. Spin-coating at a rate of 40 ^캜 and heating for 12 hours on a hot plate at 40 캜 to prepare a polyaniline / carbon nanotube nanocomposite thin film having a thickness of about 650 nm.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The prepared dye-sensitized solar cell had a power conversion efficiency of 5.71%.

The polyaniline / carbon nanotube nanocomposite prepared by adding 5 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dissolved in meta-cresol and chloroform. Spin-coating at a rate of 40 ^캜 and heating for 12 hours on a hot plate at 40 캜 to prepare a polyaniline / carbon nanotube nanocomposite thin film having a thickness of about 650 nm.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The prepared dye-sensitized solar cell had a power conversion efficiency of 7.45%.

The polyaniline / carbon nanotube nanocomposite prepared by adding 10 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dissolved in meta-cresol and chloroform. Spin-coating at a rate of 40 ^캜 and heating for 12 hours on a hot plate at 40 캜 to prepare a polyaniline / carbon nanotube nanocomposite thin film having a thickness of about 650 nm.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The prepared dye-sensitized solar cell had a power conversion efficiency of 6.84%.

The polyaniline / carbon nanoparticle nanocomposite prepared by adding 5 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dropped into meta-cresol and chloroform. - 1 cm ² by drop casting method , And heated at 40 ^° C on a hot plate for 12 hours to prepare a polyaniline / carbon nanotube nanocomposite thin film having a thickness of about 15 μm.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The fabricated dye-sensitized solar cell had a power conversion efficiency of 2.19%.

The polyaniline / carbon nanotube nanocomposite prepared by adding 5 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dissolved in meta-cresol and chloroform. Spin-coating at a speed of 10 m / min and heating for 12 hours on a hot plate at 40 ^° C to produce a polyaniline / carbon nanotube nanocomposite thin film of about 2 μm thickness.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The prepared dye-sensitized solar cell was able to obtain a power conversion efficiency of 5.40%.

The polyaniline / carbon nanotube nanocomposite prepared by adding 5 wt% of carbon nanotubes to the aniline monomer in the polymerization solution was subjected to a reduction treatment, a second doping treatment, and then dissolved in meta-cresol and chloroform. Spin-coating at a rate of about 1200 nm and heating at 40 ^° C on a hot plate for 12 hours to produce a polyaniline / carbon nanotube nanocomposite thin film about 1200 nm thick.

The polyaniline / carbon nano-dot nanocomposite thin film formed on the FTO electrode was subjected to heat treatment at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwich-bonded, and an iodide redox electrolyte To complete the assembly of the dye-sensitized solar cell. The prepared dye-sensitized solar cell achieved a power conversion efficiency of 6.74%.

For comparison with the polyaniline / carbon nano-dot nanocomposite thin film, 15 μL of 0.005 mol of chloroplatinic acid hexahydrate (H ₂ PtCl ₆ · 6H ₂ O) was applied on the FTO electrode and heat treatment at 400 ^° C. for 30 minutes To produce a platinum counter electrode. The prepared platinum counter electrode was heat-treated at 90 ^° C for 20 seconds using a dye-adsorbed working electrode and suline, sandwiched between the two electrodes, and an iododeposene electrolyte was inserted between the two electrodes to assemble the dye-sensitized solar cell Completed.

The fabricated dye-sensitized solar cell achieved a power conversion efficiency of 7.37%.

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Claims (7)

Adding carbon nanotubes having an average diameter of 1 to 15 nm as an nucleating agent for polyaniline polymerization to an aniline monomer solution and amide bonding using a catalyst; And
The polyaniline / carbon nanocomposite nanocomposite was polymerized using an amidine-bonded aniline monomer solution after adding the above carbon nanomolecules, and the polyaniline / carbon nanocomposite nanocomposite was dispersed in a second doping and solvent to prepare a polyaniline / carbon nanocomposite nanocomposite solution. - making a polyaniline / carbon nanotube nanocomposite thin film by casting or spin-coating; And
The method comprising the step of assembling the polyaniline / carbon nanotube nanocomposite thin film as a counter electrode for a dye-sensitized solar cell, the method comprising the steps of: preparing a porous polyaniline / carbon nanocomposite nanocomposite material and forming a counter electrode for a dye- Way. The method for producing a porous polyaniline / carbon nano-sized nanocomposite material according to claim 1, wherein a precursor of carbon nano dots used as a nucleating agent of polyaniline is a carbohydrate including citric acid, glucose and chitosan, Application method to counter electrode for solar cell. The porous polyaniline / carbon nano-sized nanocomposite material according to claim 1, wherein the method for producing carbon nano dots used as a nucleating agent of polyaniline is hydrothermal synthesis or pyrolysis of carbohydrates using microwave. METHOD AND APPLICATION METHOD FOR ELECTRODE ELECTRODE FOR DYE - SENSITIVE SOLAR CELL. The method for preparing a porous polyaniline / carbon nano-sized nanocomposite material according to claim 1, wherein boric acid is used as a catalyst for amide bonding of an aniline monomer to a carbon nano-dot, and a method for application to a counter electrode for a dye-sensitized solar cell. The method for producing a porous polyaniline / carbon nano-sized nanocomposite material according to claim 1, wherein the amount of carbon nano dots added to the aniline monomer solution is 1 wt% to 20 wt% of the aniline monomer, Application method to counter electrode. The method of claim 1, wherein the polyaniline / carbon nanotube nanocomposite solution is drop-cast on an FTO electrode to produce a polyaniline / carbon nanotube nanocomposite thin film for a counter electrode of a dye- μm to 50 μm. The present invention also relates to a method for manufacturing a porous polyaniline / carbon nano-sized nanocomposite material and a method for application to a counter electrode for a dye-sensitized solar cell. The method according to claim 1, wherein the prepared polyaniline / carbon nano-sized nanocomposite solution is spin-coated on an FTO electrode to prepare a polyaniline / carbon nano-dot nanocomposite thin film for a counter electrode of a dye- nm to 5 [mu] m, and a method of applying the porous polyaniline / carbon nanotube nanocomposite as a counter electrode for a dye-sensitized solar cell.

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