KR101515820B1 - a Method for Manufacturing Flexible Dye-Sensitized Solar Cell with Spray type which use a pre-dye-adsorbed Nanoparticle Metal Oxides and a Manufacturing Device using the Same - Google Patents

Abstract

The present invention relates to a method for manufacturing a flexible dye-sensitized solar cell which includes the steps of: a) absorbing an organic dye on the nanoparticle metal oxide with a nanoparticle type by mixing an organic dye solution with a colloidal solution of nanoparticle metal oxide; and b) generating an electrode by spraying the mixture solution of the organic dye solution and the colloidal solution of the nanoparticle metal oxide on a plastic substrate.

Description

TECHNICAL FIELD The present invention relates to a method of manufacturing a flexible dye-sensitized solar cell using a nanoparticle metal oxide having a dye adsorbed in advance and a manufacturing method using the same. Nanoparticle Metal Oxides and a Manufacturing Device using the Same}

The present invention relates to a method of manufacturing a flexible dye-sensitized solar cell using a nanoparticle metal oxide having a dye adsorbed in advance, and an apparatus for manufacturing a flexible dye-sensitized solar cell using the same.

Recently, the price of silicon solar cell module has been lowered and it is emerging as eco-friendly energy with efficiency and price competitiveness. However, silicon solar cells have problems such as rapid efficiency change, difficulty in securing transparency, and drastic decrease in efficiency in indoor use depending on the angle of incidence of sun. In order to solve such problems and to maximize efficiency, dye-sensitized solar cells are used.

This flexible dye-sensitized solar cell (DSC) has received considerable attention due to its wide potential. Flexible dye-sensitized solar cells are considered to be more suitable for indoor application programs, as well as wireless sensors and mobile electronics as well as power for building integrated photovoltaic modules. This is because, when the spectrum of the dye used in the dye-sensitized solar cell is below 600 nm, much of the spectrum matches well with the spectrum of indoor light sources such as fluorescent lamps, incandescent lamps and indirect diffused sunlight through windows. On the other hand, a significant portion of the outdoor spectrum above 600 nm is very similar to the spectrum of crystalline silicon solar cells.

These outdoor conditions can be one of the reasons for the high efficiency of silicon solar cells compared to organic solar cells. Dye-sensitized solar cells are also one of the very promising advantages for building systems. The sun's light can be made into a multicolor device by the selection of suitable dyes to absorb selective spectral regions. Another feature of dye-sensitized solar cells is their inherent flexibility and transparency. As a result, the transparency of the dye-sensitized solar cell can be higher than the transparency of the competitor, non-crystalline silicon solar cell.

However, dye-sensitized solar cells have inherent barriers in large-scale continuous production using a roll-to-roll process. The dye-sensitized solar cell was manufactured by forming a TiO ₂ paste on a FTO substrate by a screen printing method, drying and sintering the film overnight, depositing a TiO ₂ film in a solution containing an organic dye, TiO ₂ film.

However, according to the above manufacturing method, it is essential to achieve better electrical contact between the TiO ₂ nano powders through the high-temperature sintering process at 450 ° C or higher and to remove the organic binder, but at a high temperature, It is incompatible with the flexible polymer. This is because they do not allow temperatures above 150 캜.

Also, the immersion process which requires at least several hours of penetration of the dye into the pores between the TiO ₂ electrodes is also a problem. Device fabrication of dye-sensitized solar cells has used an immersion process for high-density dye molecules on the TiO ₂ surface, but unfortunately this process is not suitable for rapid production. It is also very difficult to control the amount of dye in the titanium dioxide electrode, under the same conditions as one of the important factors for device performance and reproducibility. For example, a dye of lower amounts to the TiO ₂ is causing the low current density, so much dye on TiO ₂ can cause a reduction in the performance of the device according to the self-quenching. However, except for the immersion process, there was no research or alternative process for flexible dye-sensitized solar cell devices.

Therefore, there is a need for a new manufacturing method which can solve such a problem.

KR 10-2009-0010309

The present invention relates to a new flexible dye-sensitized solar cell capable of shortening the time required for fabricating a device by using a manufacturing method that can be manufactured without a long-time immersion process, And a method for producing the same.

For the above purpose,

The present invention provides a method for preparing a nanoparticle metal nanoparticle comprising: a) mixing an organic dye solution with a colloidal solution of a nanoparticle metal oxide to cause the organic dye to be adsorbed to the nanoparticle metal oxide in nanoparticle form; And

b) spraying a mixture solution of the colloidal solution of the nanoparticle metal oxide and the organic dye solution on a plastic substrate to produce an electrode.

The present invention also provides a spraying apparatus for spraying a mixed solution of a colloidal solution of a nanoparticle metal oxide and an organic dye solution; And

And a gas injecting part for adjusting an injecting direction of the mixed solution,

Wherein the nanoparticle metal oxide of the mixed solution is preliminarily adsorbed in the form of nanoparticles on the dye-sensitized solar cell.

According to the method for producing a flexible dye-sensitized solar cell of the present invention,

It is possible to mass-produce the device by shortening the production time of the device significantly compared to the conventional technique in which the dye is to be adsorbed for a long period of time. In contrast to the prior art in which the adsorption amount can not be controlled, It is possible to control the dye adsorption amount by spraying the dye and the metal oxide onto the plastic substrate by the spraying method.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a titanium oxide suspension according to the content of dye.
2 is a graph showing the PCE value according to the thickness of the titanium oxide electrode of the present invention.
3 is a schematic diagram of a method of manufacturing a flexible dye-sensitized solar cell according to the present invention.
4 is a photograph showing an example of a flexible dye-sensitized solar cell manufactured according to Example 1. Fig.
5 is an SEM photograph of the surface of a flexible dye-sensitized solar cell according to Example 1 and Comparative Example 1. FIG.

Hereinafter, a method of manufacturing the flexible dye-sensitized solar cell of the present invention will be described in detail.

In the method of manufacturing a flexible dye-sensitized solar cell of the present invention,

a) mixing an organic dye solution in a colloidal solution of nanoparticulate metal oxide to cause the organic dye to be adsorbed to the nanoparticle metal oxide in nanoparticle form; And

b) injecting a mixed solution of the colloidal solution of the nanoparticle metal oxide and the organic dye solution onto a plastic substrate to produce an electrode.

Conventional studies on the preparation of dye-sensitized solar cells using spray coating techniques have shown that polymer nanofibers embedded in TiO ₂ , hydrothermally synthesized nanoparticles, Li-doped NiO films, carbon nanotubes, cobalt nano- ) Were used to focus on producing electrodes at low temperatures. However, the present invention proposes a new simple manufacturing method of a dye-sensitized solar cell using a pretreatment technique of a dye by taking advantage of spray as a deposition method.

Hereinafter, a method of manufacturing a flexible dye-sensitized solar cell according to the present invention will be described.

First, a method of manufacturing a flexible dye-sensitized solar cell according to the present invention includes a step of mixing an organic dye solution with a colloid solution of a nanoparticle metal oxide so that the organic dye is adsorbed to the nanoparticle metal oxide in the form of nanoparticles .

The method for manufacturing a flexible dye-sensitized solar cell according to the present invention uses a metal oxide coated with an organic dye by pretreating an organic dye with a nanoparticle metal oxide, and is formed on a substrate by using, for example, a flexible indium-tin oxide coated polyethylene Prior to being sprayed onto the phthalate (ITO-PEN), a dye-coated metal oxide electrode can be readily prepared using an organic dye-coated metal oxide. At this time, the amount of the dye on the metal oxide electrode can be controlled by the amount of the dye solution mixed with the metal oxide nanopowder.

The metal oxide is preferably at least one selected from the group consisting of TiO ₂ , ZnO, and NiO.

The organic dye is preferably one selected from the group consisting of a ruthenium dye, a thiophene dye, a carbazole dye, and a phenylamine dye.

There are no particular restrictions on the ruthenium dye as long as it is an organic dye containing ruthenium.

There are no particular restrictions on the thiophene dye as long as it is an organic dye containing thiophene.

There is no particular limitation as long as it is an organic dye containing carbazole as the carbazole dye.

There are no particular limitations on the organic dye as long as it is an organic dye containing phenylamine as the phenylamine dye.

It is most preferable that the content ratio of the organic dye to the nanoparticle metal oxide is 3 to 7% by weight, which is absorbed by the metal oxide nanoparticles without loss of the dye. If the content ratio of the organic dye is less than 3% by weight, sufficient adsorption can not be achieved. If the content exceeds 7% by weight, the dye-coated metal oxide nanoparticles are pale and dark black.

The plastic substrate is not particularly limited, but is preferably one selected from the group consisting of indium-tin oxide coated polyethylene naphthalate (ITO-PEN) and polyethylene terephthalate (ITO-PET).

Thereafter, the manufacturing method of the flexible dye-sensitized solar cell of the present invention includes a step b) of spraying a mixed solution of the colloidal solution of the nanoparticle metal oxide and the organic dye solution onto a plastic substrate to produce an electrode.

Since the dye-coated metal oxide electrode can be prepared immediately after the dye is pre-adsorbed to the nanoparticle metal oxide as described above, a long-time immersion process as in the prior art is not necessary, The production of the oxide electrode is also simplified.

Therefore, the dye-sensitized solar cell electrode manufactured by the manufacturing method of the present invention can easily form a dye-sensitized solar cell electrode on ITO-PEN in a size of 10 cm X 1 cm in less than 20 minutes have.

The method of manufacturing a flexible dye-sensitized solar cell of the present invention is a method of manufacturing a flexible dye-sensitized solar cell in which high-quality nanoparticles having good mechanical stability and high electrical conductivity, considering mass production of a flexible dye-sensitized solar cell by a roll- For the production of the metal oxide, it may further comprise step c) of high pressure treatment.

In the present invention, a CIP (Cold Isotactic Pressure) process may be preferably used as the high-pressure process in the step c). It is known that the physical property values of the metal oxide electrode produced by the CIP process are compatible with the requirements of a flexible dye-sensitized solar cell without organic binder and heat treatment. The pressure of the CIP process is preferably 100 to 300 MPa.

In addition, the present invention provides an apparatus for manufacturing a flexible dye-sensitized solar cell for the above manufacturing method.

The manufacturing apparatus includes a spraying unit for spraying a mixed solution of a colloidal solution of a nanoparticle metal oxide and an organic dye solution; And

And a gas injecting part for adjusting an injecting direction of the mixed solution,

And the organic dye is previously adsorbed in the nanoparticle metal oxide of the mixed solution in the form of nanoparticles. A schematic view of the manufacturing apparatus is shown in Fig.

The apparatus according to the present invention takes a method of spraying a mixed solution of a colloidal solution of a nanoparticle metal oxide and an organic dye solution, for example, as shown in Fig. That is, a colloid solution of a nanoparticle metal oxide and an organic dye solution are preliminarily mixed and the organic dye is adsorbed to the nanoparticle metal oxide in the form of nanoparticles in advance, and the nanoparticle is sprayed to form a film on the conductive polymer film (ITO-PEN) . At this time, the direction of injection is controlled by using gas. The gas may be, but not limited to, ordinary air, carbon dioxide, helium, nitrogen and the like, and most preferably nitrogen.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims.

Example

Example : flexible  Manufacture of dye-sensitized solar cell

[Example 1]: Pretreatment dye adsorption process

After loading the P- 25 (TiO ₂₎ Suspensions of 0.658g in 25g of ethanol, were added to N719 of 16.5mg (2.5%), 33mg ( 5.0%), 49.5mg (7.5%) and 66mg (10.0%) , And a dye adsorbed to the TiO ₂ nano powder was immediately obtained. The four dyes are shown in Fig.

At this time, as N719 is added to the TiO ₂ colloid solution, the TiO ₂ nanoparticles immediately change from white to pink, which is due to the adsorption of the dye.

Thus, the reason that the long time required for the immersion process, not the time at which the dye is adsorbed on the TiO ₂ nanoparticles, dyes will be understood that it would related to deep passage of the TiO ₂ electrode through the pores of the TiO ₂ nano powder there was. Figure 1 shows that 7.5 and 10 wt% dye coated TiO ₂ nanoparticles each have a pale, dark black color due to the dye remaining in the solution. On the other hand, 2.5 wt% dye-coated TiO ₂ shows relatively clear pink hue compared to 5 wt% TiO ₂ nanoparticles due to the small amount of dye in the TiO ₂ nanoparticles.

A 5 wt% pretreated coating dye in the TiO ₂ nanopowder only gave a saturated suspension homogenous to the dye remaining in the solution. This result means that the dye is completely absorbed by TiO ₂ nanoparticles without loss.

Thus, in Example 1, a flexible TiO ₂ electrode was prepared by spraying ITO-PEN at 100 ° C. using a mixed solution containing 5 wt% dye-coated TiO ₂ nanoparticles. The injection direction was controlled using nitrogen gas during the injection. After this treatment, the TiO ₂ coated with 2, 4, 6, 8, 10 and 18 um dye was obtained by controlling the deposition of a large number of multilayer films by CIP process at 200 Mpa for 10 min. The resulting flexible TiO ₂ electrode is shown in Fig.

The dye-coated TiO ₂ electrode was immersed in a CH ₂ Cl ₂ solution followed by an ethanol solution for 1 hour to test the decomposition of the dye during the CIP process before the apparatus was fabricated, There was no change in the color of each solution.

Thereafter, an electrolyte solution containing 0.04 M of I ₂ , 0.4 M of tetrabutylammonium iodide, 0.4 M of lithium iodide and 0.3 M of N-methylbenzimidazole was added to a solvent in which acetonitrile and 3-methoxypropionitrile were mixed at a volume ratio of 1: 1 , A dye-sensitized solar cell was constructed by bonding Pt / ITO-PEN to dye-coated TiO ₂ / ITO-PEN. The electrolyte was filled between the electrodes by capillary action.

[ Comparative Example  One]: Submerged  Dye adsorption process

A flexible TiO ₂ electrode was prepared using ITO-PEN (size: 10 cm * 1 cm) at a spray rate of 0.2 ml / min at 100 ° C using 2.5 wt% TiO ₂ (P-25 nano powder) in EtOH. At this time, the multi-depositions were continuously performed until a TiO ₂ electrode having a thickness of 30 μm was obtained. The TiO ₂ electrode thus prepared was sealed in a plastic bag under vacuum and then treated by CIP at 200 MPa for 10 minutes. By the above CIP treatment, the thickness of the TiO ₂ film was reduced by about 1/3 (about 10 탆) compared to that before the CIP treatment. A flexible TiO ₂ electrode produced by such a spray deposition is shown in FIG.

After this, a flexible TiO ₂ electrode on ITO-PEN was immersed in 0.1 mM N719 ethanol solvent overnight to make a dye-coated TiO ₂ electrode on ITO-PEN. After that, 0.04M of I2, 0.4M of 4-tert-butylpyridine, 0.4M of lithium iodide and 0.3M of N-methylbenzimidazole were added to the solvent in which acetonitrile and 3-methoxypropionitrile were mixed in a volume ratio of 1: The dye-sensitized solar cell was constructed by bonding Pt / ITO-PEN to dye-coated TiO ₂ / ITO-PEN in the electrolyte solution. The electrolyte was filled between the electrodes by capillary action.

Experimental Example

Confirmation of performance of dye-sensitized solar cell

1) Performance comparison according to thickness

In Example 1, dye-coated TiO ₂ electrodes of 2, 4, 6, 8, 10 and 18 μm were prepared by controlling the deposition of a large number of multilayer films after the CIP process, The device performance of the photovoltaic cell was measured immediately in the open cell structure between Pt / ITO-PEN and dye-coated TiO ₂ / ITO-PEN without proper sealing, and the PCE value was obtained and is shown in FIG.

As shown in Fig. 2, the performance of the device generally increased from 2% to 3.4% with increasing thickness, and began to decrease when it exceeded 10 탆. It can be seen that the best film thickness is 8 ~ 10 um, which is 3.4% of PCE.

2) Comparison of the performance of the solar cells of Examples and Comparative Examples

The device performance of the dye-sensitized solar cell manufactured in Example 1 and Comparative Example 1 having the same thickness of TiO ₂ film of 8 μm was evaluated by using a suitable seal between Pt / ITO-PEN and dye-coated TiO ₂ / ITO- The results are shown in Table 1 immediately after measurement in an open cell structure.

Film thickness (탆) V _oc (mV) J _sc (mA / cm ² ) ff PCE (%) Comparative Example 1 8 736 10.9 0.59 4.7 Example 1 8 648 8.10 0.65 3.4

The flexible dye-sensitized solar cell device manufactured in Example 1 has a short-circuit photocurrent density (Jsc) of 8.1 mA / cm 2, an open-circuit voltage (Voc) of 648 mV, a fill factor ) Was 0.65 and the photo-conversion efficiency (PCE) was 3.4%.

The flexible dye-sensitized solar cell device manufactured in Comparative Example 1 had a short-circuit photocurrent density (Jsc) of 10.9 mA / cm2, an open-circuit voltage (Voc) of 736 mV, factor was 0.59 and the photo-conversion efficiency (PCE) was 4.7%.

In addition, the surface images (a and b) of the dye-coated TiO ₂ prepared in Comparative Example 1 and the surface images (c and d) of the dye-coated TiO ₂ prepared in Example 1 were observed through a scanning electron microscope It is photographed and shown in Fig.

From the above results, the efficiency of Example 1 reached 73% of the efficiency of the device made by the conventional immersion process.

That is, a flexible dye-sensitized solar cell device manufactured by the present invention has the slightly lower efficiency than that prepared by the conventional dipping process of the present invention does not require a long time for the immersion process, TiO ₂ electrode From this point of view, it can be seen that the spray coating process of the present invention is very promising for mass production and large area device manufacturing, in that it does not require a high temperature sintering process for manufacturing.

Claims (11)

a) mixing an organic dye solution with a colloidal solution of a nanoparticle metal oxide to cause the organic dye to be adsorbed to the nanoparticle metal oxide in the form of nanoparticles, wherein the ratio of the organic dye to the nanoparticle metal oxide is from 3.0 to 7.0 wt% %, ≪ / RTI > And
b) spraying a mixture solution of the colloidal solution of the nanoparticle metal oxide and the organic dye solution onto a plastic substrate to produce an electrode.
The method according to claim 1,
Wherein the metal oxide is at least one selected from the group consisting of TiO ₂ , ZnO, and NiO.
The method according to claim 1,
Wherein the organic dye is any one or more selected from the group consisting of ruthenium dyes, thiophene dyes, carbazole dyes and phenylamine dyes. Type solar cell. delete The method according to claim 1,
c) subjecting the resulting mixture to high-pressure treatment.
The method according to claim 1,
Wherein the high-pressure treatment in step c) is a CIP (cold isotactic pressure) process.
The method of claim 6,
Wherein the pressure of the CIP process is 100 to 300 MPa. A jetting section for jetting a mixed solution of a colloidal solution of nanoparticle metal oxide and an organic dye solution; And
And a gas injecting part for adjusting an injecting direction of the mixed solution,
Wherein an organic dye is previously adsorbed to the nanoparticle metal oxide of the mixed solution in the form of nanoparticles in an amount of 3.0 to 7.0% by weight based on the nanoparticle metal oxide.
The method of claim 8,
Wherein the metal oxide is at least one selected from the group consisting of TiO ₂ , ZnO, and NiO.
The method of claim 8,
Wherein the organic dye is any one or more selected from the group consisting of ruthenium dyes, thiophene dyes, carbazole dyes and phenylamine dyes. Type solar cell.
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