KR101042096B1 - Dye-sensitized solar cell and method for manufacturing TiO2-CNT paste therefor - Google Patents

Abstract

According to the present invention, a first electrode through which sunlight is transmitted, a second electrode disposed to be spaced apart from the first electrode, and disposed on the first electrode, and dye is adsorbed, are nanoporous TiO _2. And a semiconductor layer having a mixed structure of carbon nanotubes and an electrolyte, and an electrolyte filled in a space between the semiconductor layer and the second electrode, wherein the carbon nanotubes have a carboxyl group formed by an acid treatment. Provide a battery.

Therefore, in the semiconductor layer, the carboxyl group of the carbon nanotubes is bonded to O of TiO ₂ , and the carbon nanotubes connect the spaces between the particles in the porous TiO ₂ . From this, since the electron mobility in the semiconductor layer is improved, the performance (Voc, Jsc, Fill Factor, efficiency) of the dye-sensitized solar cell is improved.

Description

Dye-sensitized solar cell and method for manufacturing TiO2-CNT paste therefor}

The present invention relates to a method for producing TiO ₂ -carbon nanotube paste for dye-sensitized solar cells and dye-sensitized solar cells, and more particularly, to TiO ₂ -carbon nano for dye-sensitized solar cells and dye-sensitized solar cells with improved efficiency. The present invention relates to a tube paste manufacturing method.

Recently, various studies have been conducted on alternative energy sources that can replace existing fossil fuels to solve energy problems. In particular, extensive research has been conducted to utilize natural energy such as wind and solar power. Of these, solar cells using solar power have received the most attention as alternative energy sources because the amount of resources is infinite and environmentally friendly. There are various types of solar cells, of which crystalline silicon solar cells have the highest market share.

However, since the crystalline silicon solar cell has a high manufacturing cost and has many limitations in improving efficiency, development of a dye-sensitized solar cell having a low manufacturing cost as an alternative has been actively conducted.

Unlike silicon solar cells, dye-sensitized solar cells are composed of photosensitive dye molecules capable of absorbing visible light to produce electron-hole pairs, and transition metal oxides for transferring generated electrons. Is a photoelectrochemical solar cell.

However, in such a dye-sensitized solar cell, the generated electrons are moved to the TiO ₂ layer conduction band, and since the mobility of electrons in the TiO ₂ layer itself is limited, the efficiency improvement of the dye-sensitized solar cell is limited. There is this.

An object of the present invention is to provide a dye-sensitized solar cell and a TiO ₂ -carbon nanotube paste for dye-sensitized solar cell with improved efficiency.

According to the present invention, a first electrode through which sunlight is transmitted, a second electrode disposed to be spaced apart from the first electrode, and disposed on the first electrode, and dye is adsorbed, are nanoporous TiO _2. And a semiconductor layer having a mixed structure of carbon nanotubes and an electrolyte, and an electrolyte filled in a space between the semiconductor layer and the second electrode, wherein the carbon nanotubes have a carboxyl group formed by an acid treatment. Provide a battery.

According to another aspect of the invention, the present invention, in the method for producing a dye-sensitized solar cell TiO ₂ -carbon nanotube paste, the carbon nanotubes are acid-treated to generate a carboxyl group, and the carbon nano-carbon produced carboxyl group by acid treatment for the carbon nanotube paste TiO ₂ - - the dispersed TiO ₂ comprising the steps of manufacturing the carbon nanotube paste, - the tube with the porous nanoparticle TiO ₂ powder were mixed in a solvent dispersed TiO ₂ the carbon nanotube paste It provides a TiO ₂ -carbon nanotube paste manufacturing method for a dye-sensitized solar cell comprising the step of preparing.

The dye-sensitized solar cell and the TiO ₂ -carbon nanotube paste manufacturing method for the dye-sensitized solar cell according to the present invention have the following effects.

First, in the semiconductor layer, the carboxyl group of the carbon nanotubes is bonded to O of TiO ₂ , and the carbon nanotubes connect the spaces between the particles in the porous TiO ₂ . Therefore, since electron mobility is improved in the semiconductor layer, the performance (Voc, Jsc, Fill Factor, efficiency) of the dye-sensitized solar cell is improved.

Second, when the dye-sensitized solar cell further includes a TiO ₂ blocking layer having an anatase structure, the dye absorbs sunlight and the electrons generated are returned to the dye or the electrolyte. Since this is blocked by the TiO ₂ blocking layer, the performance of the dye-sensitized solar cell is improved. Furthermore, when the TiO ₂ blocking layer is manufactured by spin coating, the interface property between the first electrodes is improved, and thus the electron mobility from the semiconductor layer to the first electrode is improved. Therefore, the performance of the dye-sensitized solar cell is further improved.

1 is a schematic structural diagram of a dye-sensitized solar cell 100 according to an embodiment of the present invention. Referring to FIG. 1, the dye-sensitized solar cell 100 includes a first substrate 110 and a second substrate 120 disposed to be spaced apart from each other. Solar light is incident on the first substrate 110 to transmit light, and the first substrate 110 is formed of a transparent material so that the transmittance of the sunlight is increased. Examples of the transparent material include glass or transparent plastic. As the transparent plastic, acrylic resins, polyesters, polycarbonates, polyethylenes, polyethersulfones, olefin maleimide copolymers, norbornene-based resins, and the like may be used. Preferably, polyethylene naphthalate or polyethylene terephthalate may be used. have.

The first electrode 130 is formed on the first substrate 110 to face the second substrate 120. The first electrode 130 is formed of a transparent material, and there are ITO, FTO, and the like. The second electrode 140 is formed on the second substrate 120 to face the first substrate 110. The second electrode 140 is formed of a material having excellent conductivity such as platinum.

A TiO ₂ blocking layer 150 having an anatase structure is formed on the first electrode 130. The anatase structure TiO ₂ blocking layer 150 has a photocatalytic property that is significantly higher than that of the rutile structure. For example, the electrons exhibit 89 times faster charge mobility in the anatase structure than in the rutile structure. Furthermore, the TiO ₂ layer of the anatase structure has excitation light having a band gap energy of 3.2 eV or less (380 nm), and the TiO ₂ layer of the rutile structure has a wavelength of 415 nm or less, corresponding to 3.0 eV. The wavelength becomes excitation light. Therefore, since the anatase structure absorbs light in a wider wavelength band than the rutile structure, the anatase structure can exhibit excellent solar cell performance compared to the rutile structure.

The TiO ₂ blocking layer 150 is formed by spin coating. The interface of the first electrode 130 is not smooth, and when in contact with the electrolyte 180, an electron transfer phenomenon occurs to prevent smooth movement of electrons. However, when the TiO ₂ blocking layer 150 is formed by spin coating, the TiO ₂ blocking layer 150 smoothly fills the interface of the first electrode 130 to increase mobility of electrons. In addition, the TiO ₂ blocking layer 150 blocks contact between the electrolyte 180 and the first electrode 130 to suppress the electron return phenomenon. From this, the efficiency of the dye-sensitized solar cell 100 is improved. Detailed description will be described later.

Since the network characteristics between the crystals in the TiO ₂ blocking layer 150 are improved, the mobility of electrons is further improved. In particular, the spin coating method, unlike the sputtering method, has the advantage of low manufacturing cost and large area manufacturing.

The semiconductor layer 160 is formed on the TiO ₂ blocking layer 150. The semiconductor layer 160 has a structure in which porous nanoparticles (nanoporous) TiO ₂ and carbon nanotubes are mixed. In the semiconductor layer, the TiO ₂ has anatase and rutile structures.

The carbon nanotubes are multi-walled carbon nanotubes (MWCNTs). Generally, carbon nanotubes are divided into single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled carbon nanotubes. The diameter of the single wall carbon nanotubes is about 0.6-1.8 nm, and the diameter of the multi-wall carbon nanotubes is about 10-100 nm. Although single-wall carbon nanotubes have excellent electron mobility compared to multi-wall carbon nanotubes, multi-wall carbon nanotubes are very inexpensive compared to single-wall carbon nanotubes. In the present embodiment, even if a multi-wall carbon nanotube is used as the carbon nanotubes, the efficiency of the dye-sensitized solar cell is improved. The solar cell efficiency is expected to be further improved.

The dye 170 is adsorbed to the porous nanoparticle TiO ₂ layer 160. The dye 170 is electron-transfer from the ground state to the excited state by absorbing light to form an electron-hole pair, the electrons in the excited state is injected into the semiconductor layer conduction band and then the first electrode 130 and the first The electromotive force is generated while moving to the second electrode 140. The dye 170 may be used without limitation as long as it is generally used in the field of solar cells, ruthenium complex may be used. However, the present invention is not limited thereto.

The electrolyte 180 is filled as an electrolyte in a space between the porous nanoparticle TiO ₂ layer 160 and the second electrode 140. As the electrolyte 180, an acetonitrile solution of iodine, a NMetyl-2-pyrrolidone (NMP) solution, a 3-methoxypropionitrile solution, and the like may be used, but the present invention is not limited thereto.

In the semiconductor layer 160, the carbon nanotubes not only have high electrical conductivity (about 1000 times that of copper), but also further improve electron mobility by connecting spaces between particles in the porous TiO ₂ . This will be described in more detail below.

In the semiconductor layer 160, the carbon nanotubes have a carboxyl group (COOH) formed by acid treatment. In general, in the dye-sensitized solar cell, the carboxyl group of the dye and O of TiO ₂ are bonded to each other, and the excited electrons have a structure in which they move to TiO ₂ . However, in the semiconductor layer 160, the carboxyl group of the carbon nanotubes is combined with O of TiO ₂ , and the excited electrons are moved back to the carbon nanotubes through TiO ₂ , and from this, the carbon nanotubes themselves. The high electrical conductivity of and the spatial connection between the particles in the porous TiO ₂ further enhances the mobility of the electrons. By the electron mobility improvement, the efficiency of the dye-sensitized solar cell 100 is improved.

Referring to Figure 2, it will be described with reference to the manufacturing method of the TiO ₂ blocking layer 150.

First, isopropphenol in which titanium tetraisopropoxide (Ti (OC ₃ H ₇ ) ₄ is mixed with 1.0 M of isopropphenol (C ₃ H ₇ OH) mixed with 1.0 M, and hydrochloric acid (HCl) is mixed in 0.8 M. 100 ml is prepared (step S110, step S120), mixed with each other and stirred for 24 hours (step S130) to form a transparent sol (step S140).

The transparent sol is spin coated on the first substrate on which the first electrode is formed (S150). The spin coating is performed at 500 rpm, 1000 rpm, 2000 rpm for about 60 seconds each. Then, the spin-coated sol is dried for about 1 hour at 100 ° C (step S160), and then sintered at 450 ° C for 30 minutes (step S170). Through this, the TiO ₂ blocking layer 150 is formed on the first electrode 130. By the sintering, the TiO ₂ blocking layer 150 has an anatase structure.

3 shows X-ray diffraction pattern data of the TiO ₂ blocking layer 150 performed using XRD. Referring to FIG. 3, it can be seen that the TiO ₂ blocking layer 150 has an anatase structure.

4 (a) to 4 (c) are SEM micrographs of the TiO ₂ blocking layer 150 manufactured by the spin coating method. Figure 4 (a) ~ (c) shows the spin-coated state at 2000rpm, 1000rpm, 500rpm respectively. The TiO ₂ blocking layer 150 has a thickness of 10 to 30 nm when spin coated at 2000 rpm, is formed with a thickness of 40 to 60 nm when spin coated at 1000 rpm, and 120 to 150 nm when spin coated at 500 rpm. It is formed in thickness. That is, as the rotation speed is smaller, the thickness of the TiO ₂ blocking layer 150 becomes thicker, stable crystal formation is possible, and network characteristics between the crystals are improved. As described above, when the network characteristics are improved, the mobility of electrons increases, so that the efficiency of the dye-sensitized solar cell increases.

5 wherein the TiO ₂ blocking layer 150, the dye-sensitized, and a solar cell Jsc (short-circuit current) showing the efficiency characteristics of the experimental data is shown, wherein the TiO ₂ blocking layer in Figure 6 (150 according to the Experimental data of the efficiency according to the thickness of is shown. In FIGS. 5 and 6, the semiconductor layer 160 is a TiO ₂ layer having a general anatase structure without mixing general carbon nanotubes.

5 and in Figure 6, (without the TiO ₂ blocking layer 150), the thickness of the TiO ₂ blocking layer 150 is 0㎚, 10 ~ 30㎚ (If the spin coated with 2000rpm), 40 ~ 60 Nm (if spin-coated at 1000 rpm) and 120-150 nm (when spin-coated at 2000 rpm). Table 1 also summarizes experimental data of open-circuit voltage (Voc), Jsc, Fill Factor, and efficiency according to the thickness of the TiO ₂ blocking layer 150. In order to show the effect of the TiO ₂ blocking layer 150, in FIG. 5, FIG. 6 and Table 1, the semiconductor layer 160 has a structure of a porous nanoparticle TiO ₂ layer having a general anatase structure.

Referring to FIGS. 5, 6 and Table 1, when the TiO ₂ blocking layer 150 is present, it can be seen that Voc, Jsc, Fill Factor, and efficiency are all improved. The performance improvement of the solar cell is caused by the TiO ₂ blocking layer 150 suppressing back transfer of electrons by blocking contact between the first electrode 130 and the electrolyte 180. Looking at this in detail as follows.

[Table 1] Performance Comparison of Dye-Sensitized Solar Cell According to the Thickness of TiO ₂ Blocking Layer 150

Of the TiO ₂ blocking layer 150
Thickness (nm) Voc (V) Jsc (㎃ / ㎠) Fill factor efficiency (%) 0 0.725 7.934 0.668 3.78 10-30 0.725 8.349 0.679 4.08 40-60 0.725 8.618 0.694 4.27 120-150 0.725 9.283 0.698 4.62

Herein, the porous nanoparticle TiO ₂ layer is 13 nm (formed using Solaronix's Ti-Nanoxide T / SP).

Referring to FIG. 1, the dye 170 absorbs sunlight to generate an electron-hole pair. The generated electrons exit the external circuit through the semiconductor layer 160, the TiO ₂ blocking layer 150, and the first electrode 130, and then flow through the second electrode 140 again. It has a circular structure. In FIG. 1, a solid arrow P1 shows a movement path of the generated electrons. However, in the related art, a phenomenon in which some of the generated electrons return to the electrolyte 180 and the dye 170 again occurs (see dotted arrow P2 in FIG. 1). This return phenomenon caused a decrease in the performance of the solar cell. However, in this embodiment, since the return electrons are blocked by the TiO ₂ blocking layer 150, the performance of the dye-sensitized solar cell 100 is improved. Furthermore, since the interface property between the TiO ₂ blocking layer 150 and the first electrode 130 is improved, the generated electrons move from the semiconductor layer 160 to the first electrode 130. Is improved. Therefore, due to the improvement of electron mobility, the performance of the dye-sensitized solar cell 100 is further improved.

Referring to FIG. 6, the greater the thickness of the TiO ₂ blocking layer 150, the higher the efficiency. However, when the thickness of the TiO ₂ blocking layer 150 exceeds 650 nm, the movement of electrons moving from the semiconductor layer to the first electrode is suppressed, and the efficiency tends to be reduced. Therefore, the TiO ₂ blocking layer preferably has a thickness of 0 to 650 nm.

FIG. 7 is a flowchart sequentially showing a method of preparing a TiO ₂ -carbon nanotube paste for manufacturing the semiconductor layer. Referring to FIG. 7, the manufacturing method comprises the steps of acid-treating carbon nanotubes to generate carboxyl groups (step S200), and preparing TiO ₂ -carbon nanotube pastes using the acid-treated carbon nanotubes ( S300 step). It demonstrates in detail below.

First, an acid treatment of carbon nanotubes to generate a carboxyl group (step S200) is as follows. Prepare 0.5 g of multi-wall carbon nanotube powder and 150 ml of HNO ₃ solution (step S210). The multi-wall carbon nanotube powder and the HNO for about 18 hours while refluxing at about 160 ° C. ₃ Mix the solution to prepare a mixture. (S220 step)

The mixture is filtered using a PTFE (poly tetrafluoroethylene) membrane while maintaining about PH 7. (Step S230) Since the mixture is acidic, and mixed with dilute water and dilute NaOH solution to the mixture is filtered while neutralizing the mixture. The filtered carbon nanotube powder is dried at about 80 ° C. for about 1 hour. (S240 step) Through the above process, a carboxyl group is generated in the multi-wall carbon nanotube.

The step of preparing a TiO ₂ -carbon nanotube paste using the acid treated carbon nanotubes (step S300) is as follows. First, 10 g of the porous nanoparticle TiO ₂ powder and the acid-treated multi-walled carbon nanotube powder are prepared. (Step S310) The acid-treated multi-walled carbon nanotube powder and the porous nanoparticle TiO _{2 are prepared.} Mixing ratio of the powder may be selected in various ways, in this embodiment, the acid-treated multi-walled carbon nanotube powder is prepared in 0.05g, 0.1g, 0.2g, respectively.

The acid-treated multi-walled carbon nanotube powder and the porous nanoparticle TiO ₂ powder are placed in a TiO ₂ dispersion apparatus. In this embodiment, ARE-250 is used as the dispersing device. 35 ml of ethanol and 20 ml of distilled water were added to the dispersion apparatus as a solvent. Then, using the dispersing apparatus, a mixed TiO ₂ -carbon nanotube paste is prepared by repeatedly mixing the deforming process for 1 minute 5 times after mixing for 1 minute (step S320).

Thereafter, the dispersed TiO ₂ -carbon nanotube paste is acid treated. The acid treatment is carried out by mixing 10 g of the dispersed TiO ₂ -carbon nanotube paste and 0.2 ml of HCL or HNO ₃ at room temperature for 4 hours. By the acid treatment, the TiO ₂ -carbon nanotube paste finally used for forming the semiconductor layer is completed.

FIG. 8A shows a picture of the TiO ₂ -carbon nanotube (using multi-wall carbon nanotube) paste without performing the acid treatment step, and FIG. 8B shows the TiO ₂ -carbon having the acid treatment step performed according to the present embodiment. A photo of the nanotube paste is shown. Referring to Figure 8a, the acid-treated multi-walled carbon nanotubes, the average diameter is 10 ~ 15nm, has a long elongated structure. However, referring to Figure 8b, the acid-treated multi-wall carbon nanotubes, the average diameter is 50 ~ 100nm, the length is cut by the acid treatment is very short.

9A is a sintered surface photograph of TiO ₂ -carbon nanotubes (using multi-walled carbon nanotubes) without performing an acid treatment step. In the picture, the round shape is TiO ₂ , and the long cylindrical shape is carbon nanotube. 9B and 9C are sintered photographs of TiO ₂ -carbon nanotube pastes subjected to an acid treatment step according to the present embodiment. 10A is a sintered cross-sectional photograph of a TiO ₂ -carbon nanotube paste in which an acid treatment step is performed according to this embodiment, and FIG. 10B is an enlarged photograph of FIG. 10A.

As shown in FIG. 9B, the carbon nanotubes show TiO ₂ . In addition, as shown in 9b, the carbon nanotubes show a state connecting the cracks between TiO ₂ . That is, by having a structure in which the carboxyl groups of the carbon nanotubes formed by dispersing are bonded to O of TiO ₂ , the electrical conductivity of the TiO ₂ -carbon nanotube paste is improved. In addition, by connecting the cracks between the TiO ₂ carbon nanotubes, it serves to promote the mobility of electrons.

11A is an XRD pattern graph of TiO ₂ . The crystal structure of TiO ₂ is a crystal structure in which the anatase structure and the rutile structure are present simultaneously in a ratio of about 7: 3. In Fig. 11A,? Indicates the main peak of the anatase TiO ₂ structure, and? Indicates the main peak of the rutile TiO ₂ structure. Referring to FIG. 11A, it can be seen that TiO ₂ in the semiconductor layer 160 has an anatase and a rutile structure. 11B is a graph of an XRD pattern of multi-walled carbon nanotubes. 11C is a graph of the XRD pattern of the semiconductor layer 160. 11A through 11C, the semiconductor layer 160 may be a structure in which an anatase crystal structure, a rutile crystal structure, and a crystal structure of multi-wall carbon nanotubes are mixed.

12 shows experimental data of Jsc showing the efficiency improving characteristics of the dye-sensitized solar cell by the semiconductor layer 160 formed by the TiO ₂ -carbon nanotube paste in which the acid treatment step was performed according to the present embodiment. It is. In Table 2, when 0.05g, 0.1g, 0.2g of the acid-treated multi-walled carbon nanotube powder is applied in (S310 step), when HCL and HNO ₃ are used as the acid in (S330 step), respectively. Experimental data on open-circuit voltage (Voc), Jsc, Fill Factor, and efficiency are summarized. Here, the comparative example, the other configuration is the same, the TiO ₂ paste (10g TiO ₂ powder, 35ml ethanol, 20ml, distilled water 20ml, HCl 0.2ml) without the multi-wall carbon nanotubes acid-treated with the semiconductor layer 160 Is a dye-sensitized solar cell formed by

 Referring to Figure 11 and Table 2, when applying the acid-treated multi-walled carbon nanotubes 0.2g, it can be seen that all improved Voc, Jsc, Fill Factor, efficiency compared to the comparative example. The performance improvement of such a solar cell is attributable to the improvement of electron mobility in the semiconductor layer 160.

[Table 2] Performance Comparison of Dye-Sensitized Solar Cells Using Multi-Wall Carbon Nanotubes

Voc (V) Jsc
(㎃ / ㎠) Fill
Factor efficiency (%) Comparative example 0.675 6.131 0.645 2.69 Example HCl CNT (0.05 g) 0.675 2.161 0.628 0.90 CNT (0.10 g) 0.675 2.302 0.631 0.99 CNT (0.20 g) 0.675 7.596 0.700 3.54 HNO ₃ CNT (0.05 g) 0.675 2.360 0.621 1.01 CNT (0.10 g) 0.675 2.341 0.598 0.93 CNT (0.20 g) 0.675 7.598 0.672 3.39

Here, the thickness of the TiO2 blocking layer is 120 to 150 nm.

Although the present invention has been described with reference to the embodiments shown in the drawings, this is merely exemplary, and it will be understood by those skilled in the art that various modifications and equivalent other embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

1 is a schematic structural diagram of a dye-sensitized solar cell according to an embodiment of the present invention.

FIG. 2 is a flowchart illustrating a method of manufacturing the TiO ₂ blocking layer shown in FIG. 1 step by step.

FIG. 3 is graphs showing X-ray diffraction pattern data of the TiO ₂ blocking layer shown in FIG. 1 using XRD.

4 (a) to 4 (c) are SEM micrographs of the TiO ₂ blocking layer of FIG. 1 prepared by spin coating.

FIG. 5 is an experimental graph of short-circuit current (Jsc) showing efficiency improvement characteristics of a dye-sensitized solar cell by the TiO ₂ blocking layer shown in FIG. 1.

6 is an experimental graph of efficiency according to the thickness of the TiO ₂ blocking layer illustrated in FIG. 1.

FIG. 7 is a flowchart sequentially showing an embodiment of a TiO ₂ -carbon nanotube paste manufacturing method for manufacturing the semiconductor layer shown in FIG. 1.

FIG. 8A is a sintered picture of a TiO ₂ -carbon nanotube (using multi-wall carbon nanotube) paste which has not been subjected to an acid treatment step, and FIG. 8B is a TiO _{2 having} been subjected to an acid treatment step according to one embodiment of FIG. 7. -Sintered picture of carbon nanotube paste.

9A is a sintered surface photograph of a TiO ₂ -carbon nanotube (using multi-walled carbon nanotube) paste without performing an acid treatment step, and FIGS. 9B and 9C illustrate an acid treatment step according to an embodiment of FIG. 7. Sintered photographs of TiO ₂ -carbon nanotube pastes performed.

FIG. 10A is a sintered cross-sectional photograph of a TiO ₂ -carbon nanotube paste in which an acid treatment step is performed according to an embodiment of FIG. 7, and FIG. 10B is an enlarged photograph of FIG. 10A.

FIG. 11A is a graph showing X-ray diffraction pattern data of TiO ₂ used in the semiconductor layer shown in FIG. 1 using XRD. FIG.

FIG. 11B is a graph showing X-ray diffraction pattern data of multi-wall carbon nanotubes used in the semiconductor layer shown in FIG. 1 using XRD.

FIG. 11C is a graph showing X-ray diffraction pattern data of the semiconductor layer illustrated in FIG. 1 using XRD.

FIG. 12 is an experimental graph of Jsc showing efficiency improving characteristics of the dye-sensitized solar cell by the semiconductor layer illustrated in FIG. 1.

<Brief description of symbols for the main parts of the drawings>

100: dye-sensitized solar cell 110: the first substrate

120: second substrate 130: first electrode

140: second electrode 150: TiO ₂ blocking layer

160: semiconductor layer 170: dye

180: electrolyte

Claims (8)

delete A first electrode through which sunlight is transmitted; A second electrode spaced apart from the first electrode; A semiconductor layer disposed on the first electrode and having a structure in which a dye is adsorbed and porous nanoparticles (TiO ₂ ) and carbon nanotubes are mixed; And An electrolyte filled in a space between the semiconductor layer and the second electrode, The carbon nanotubes have a carboxyl group formed by acid treatment, A dye-sensitized solar cell is disposed between the first electrode and the semiconductor layer and further comprises a TiO ₂ blocking layer having an anatase structure. The method according to claim 2, The TiO ₂ blocking layer is spin-coated dye-sensitized solar cell formed. A first electrode through which sunlight is transmitted; A second electrode spaced apart from the first electrode; A semiconductor layer disposed on the first electrode and having a structure in which a dye is adsorbed and porous nanoparticles (TiO ₂ ) and carbon nanotubes are mixed; And An electrolyte filled in a space between the semiconductor layer and the second electrode, The carbon nanotubes have a carboxyl group formed by acid treatment, The TiO ₂ in the semiconductor layer is a dye-sensitized solar cell having an anatase and rutile (Rutile) structure. A first electrode through which sunlight is transmitted; A second electrode spaced apart from the first electrode; A semiconductor layer disposed on the first electrode and having a structure in which a dye is adsorbed and porous nanoparticles (TiO ₂ ) and carbon nanotubes are mixed; And An electrolyte filled in a space between the semiconductor layer and the second electrode, The carbon nanotubes have a carboxyl group formed by acid treatment, The carbon nanotube is a multi-walled carbon nanotube (MWCNT) dye-sensitized solar cell. In the manufacturing method of TiO ₂ -carbon nanotube paste for dye-sensitized solar cell, Acid treatment of the carbon nanotubes to generate carboxyl groups; Preparing a dispersed TiO ₂ -carbon nanotube paste by mixing the carboxyl group-generated carbon nanotubes and the porous nanoparticle TiO ₂ powder in a solvent; And A method of manufacturing a TiO ₂ -carbon nanotube paste for a dye-sensitized solar cell, comprising the step of acid-treating the dispersed TiO ₂ -carbon nanotube paste to prepare a TiO ₂ -carbon nanotube paste. The method according to claim 6, Generating the carboxyl group, Preparing a mixture by mixing carbon nanotubes and nitric acid under set conditions; And Method for producing a TiO ₂ -carbon nanotube paste for a dye-sensitized solar cell comprising the step of filtering the mixture while maintaining a set PH range using an alkaline solution and distilled water. The method according to claim 6, In the step of preparing the dispersed TiO ₂ -carbon nanotube paste, The solvent is a method for producing a TiO ₂ -carbon nanotube paste for dye-sensitized solar cells comprising ethanol and distilled water.

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