KR101302790B1 - A photoelectrode for dyes response solacell with titanium dioxide nanotube layer and a method of thereof - Google Patents

Abstract

The present invention relates to a photoelectrode for a dye-sensitized solar cell including a titanium dioxide nanotube layer and a method for manufacturing the same, and can improve electron transfer using a highly aligned titanium dioxide nanotube layer, and a large number of dyes in the porous layer of nanoparticles. Disclosed is a dye-sensitized solar cell photoelectrode including titanium dioxide nanotubes and a method of manufacturing the same, which can enhance energy conversion efficiency by allowing the adsorbent to adsorb, and anticipate light scattering effects.

Description

Photoelectrode for dyes response solacell with titanium dioxide nanotube layer and a method of

The present invention relates to a photoelectrode for a dye-sensitized solar cell including a titanium dioxide nanotube layer and a method of manufacturing the same, and more particularly, a metal oxide in the form of a highly aligned nanotube is included to increase the life time of the electron. Accordingly, a photoelectrode for a dye-sensitized solar cell including a TiO ₂ nanotube layer, which reduces the recombination of electrons, reduces electron loss, increases current, improves energy conversion efficiency, and anticipates light scattering effects. It relates to a manufacturing method thereof.

The solar cell refers to a device for converting photon energy into electrical energy, and the dual dye-sensitized solar cell is a device for producing electricity when receiving sunlight, and is composed of a photoelectrode, a counter electrode, and an electrolyte. Among the components of the solar cell is a porous membrane, the photoelectrode including the metal oxide nanoparticles is composed of n-type transition metal oxide semiconductor having a wide band cap such as TiO ₂ , ZnO, SnO ₂ , WO ₃ In general, it is prepared by applying a paste containing metal oxide nanoparticles on a conductive substrate and sintering at a high temperature.

There have been many studies on increasing energy conversion efficiency of the photoelectrode for dye-sensitized solar cell as described above, and thus economical manufacturing of solar cell.

For example, Korean Patent Publication No. 10-2008-38651 discloses a photoelectrode for a dye-sensitized solar cell including a blocking layer and a method of manufacturing the same, and includes a conductive substrate, a blocking layer on a substrate, and a glycoporous membrane on which a photosensitive dye is adsorbed. A photoelectrode for dye-sensitized solar cells is disclosed. However, the published patent is for preventing the scattering of light, which is different from the pursuit of the present invention.

In addition, Korean Patent No. 10-998146 discloses a dye-sensitized solar cell including a titanium tube and a thin plate structure, and the patent forms a titanium thin plate structure on a conductive transparent glass, and forms a titanium dioxide nanotube layer thereon. A method of making the first electrode portion is taken.

In Korean Patent Publication No. 10-2010-2442 similar to the registered patent, an n-type semiconductor layer of titanium dioxide nanopowder is used instead of the titanium dioxide nanotube layer.

Another publication 10-2011-38748 discloses a photoelectrode of a dye-sensitized solar cell to which titanium oxide nanofibers are added and a method of manufacturing the same.

In the published patent, an electrospinning solution is prepared, polymer / titanium oxide nanofibers are manufactured, and then fired to make titanium oxide nanofibers, a titanium oxide coating solution is prepared, and a photoelectrode is prepared. It is judged to be characterized by using nanofibers.

Meanwhile, Patent Publication No. 10-2011-40252 discloses a photoelectrode for dye-sensitized solar cells, a manufacturing method thereof, and the like, and in the published patent, medium-porous dioxide having an average particle diameter of 100 to 2,000 nm and a specific surface area of 150 to 300 m 2 / g. To improve the efficiency by providing a photoelectrode using titanium particles.

In addition, Korean Patent Application Publication No. 10-2011-47533 discloses a dye-sensitized solar cell that improves the photoelectron transfer speed and the light conversion efficiency by using a carbon nanotube layer as a photoelectrode. The dye-sensitized solar cell photoelectrode containing the coated silica particles was provided to provide a solar cell having increased light absorption.

Although many attempts have been made to improve the efficiency of dye-sensitized solar cells as described above, it is believed that the present invention is different from the present invention in terms of the object and structure or effects thereof.

The present invention overcomes the problems of the prior art as described above, it is possible to improve the movement of electrons by using a titanium dioxide nanotube layer of a high order, and to improve the energy conversion efficiency by allowing a large number of dyes to adsorb to the porous layer of nanoparticles. The purpose of the present invention is to provide a dye-sensitized solar cell photoelectrode including titanium dioxide nanotubes and a method of manufacturing the same, which can be expected as well as light scattering effect.

In order to accomplish the object of the present invention as described above,

Provided is a photosensitive electrode for a dye-sensitized solar cell including a porous layer capable of dye adsorption on the conductive substrate and a metal oxide layer capable of dye adsorption in the form of nanotubes on the porous layer.

The thickness of the porous layer is preferably 3 ~ 15㎛, the thickness of the metal oxide layer of the nanotube type is preferably 3 ~ 30㎛, the pore size of the nanotube type metal oxide is 10 ~ 500nm diameter. This is preferred.

In the present invention, FTO, which is stable even at high sintering temperature, is used as a conductive substrate for photoelectrode, and the nanotubes made of Ti foil are immersed in hydrogen peroxide to separate only the nanotubes, and a paste of TiO ₂ nanoparticles is prepared on the conductive substrate. The present invention provides a method of manufacturing a photoelectrode by coating by a doctor blade method and then attaching the separated nanotubes.

In the above, the coating thickness of the TiO ₂ nanoparticles is 3 ~ 15㎛, the thickness of the nanotubes is 3 ~ 30㎛, the pores of the nanotubes are preferably 10 ~ 500nm in diameter.

According to the present invention, it is possible to minimize the loss of electrons by using a nanotube-type metal oxide, which is caused by the loss of electrons caused by a poor flow of conventional electrons. In addition, as the electron's life time increases, the recombination of the electrons decreases and the loss of electrons increases, resulting in an increase in current.The highly ordered nanotubes form the electrons more smoothly than the nanoparticles. Therefore, it is possible to prevent the loss of electrons. Accordingly, the energy conversion efficiency can be improved, which means that the scattering effect of light, that is, scattering can occur in the nanotube layer so that the solar cell can receive the maximum light, and thus light passing through the nanoparticles is in the nanotube layer. It can be absorbed in a portion and scattered to absorb light once more in the nanoparticle layer can provide a solar cell that can improve the energy conversion efficiency.

1 is a schematic structural diagram of a photoelectrode of the present invention.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

The following detailed description and examples are provided to aid the practice and understanding of the present invention, but are not intended to limit the invention.

In the present invention, a porous layer of a paste of metal oxide nanoparticles is first coated on a conductive substrate, wherein the metal oxide is titanium dioxide (TiO ₂ ) and the coating thickness is 3 to 15 μm.

In the above coating thickness, since the amount of dye adsorption is small at 3 μm or less, the efficiency of the solar cell may be drastically reduced, and coating at 15 μm or more may increase the amount of dye adsorption, but the transfer path of electron transfer may be long. Since the transfer of electrons does not occur smoothly, the efficiency of the solar cell may not be good, so it is within the above range.

Then, the metal oxide in the form of nanotubes, preferably titanium dioxide nanotubes on the metal oxide nanoparticles coated on the conductive substrate, in this case, the nanotube layer is 3 ~ 30㎛. The thickness of the nanotube layer herein is also in the above range for the same reason as the thickness of the metal oxide layer.

In the above, the metal oxide of the nanotube type is preferably a pore size of 10 ~ 500nm, if the pore diameter is 10nm or less, it is very difficult to manufacture nanotubes, but the dye adsorption can be made rather In the case of more than 500 nm, the nanotubes are not robust and dye adsorption may be reduced due to a reduction in surface area. The pore size may be determined by an applied voltage and an application time when oxidizing the nanotubes.

EXAMPLES Preparation of Titanium Dioxide (TiO ₂ ) Nanotubes

(wash)

Ti foil of 0.25 mm thickness and purity of 99.6% was sonicated in distilled water and acetone.

(Electropolishing)

60% HClO ₄ (Perchloric acid), butanol and ethanol were immersed in a mixed solution mixed at a volume ratio of 1: 6: 9, and a voltage of 20 V was applied at -20 ° C for 5 minutes.

(Primary oxidation; anodization)

After washing with distilled water, it was immersed in C ₂ H ₆ O ₂ (ethylene glycol) solution containing 0.38wt% NH ₄ F (Ammonium fluoride) and 1.79wt% H ₂ O, and a voltage of 70V was applied for 6-10 hours.

Crystallization

After washing, the mixture was sintered at 480 ° C. for 30 minutes.

(Secondary oxidation; anodization)

The solution was immersed in a C ₂ H ₆ O ₂ solution containing 0.38 wt% NH ₄ F and 1.79 wt% H ₂ O, and a voltage of 10 V was applied at 20 ° C. for 10 minutes.

Removing

After soaking in 10% hydrogen peroxide for 24 hours, only titanium dioxide nanotubes were separated.

[Example]

Using the prepared titanium dioxide, a conventional solar cell was manufactured under the following conditions, and its properties were measured.

Photoelectrode manufacturing was completed by coating a paste of titanium dioxide nanoparticles on a conductive substrate by a doctor blade method and then attaching the prepared titanium dioxide nanotubes.

As can be seen in the above embodiments, when the photoelectrode using titanium dioxide nanotubes is used for the solar cell as in the present invention, it can be seen that the energy conversion efficiency is superior to that otherwise. Therefore, by using the present invention it is possible to manufacture a solar cell of the efficiency.

Claims (5)

A photosensitive electrode for a dye-sensitized solar cell comprising a porous layer made of metal oxide nanoparticles on a conductive substrate and capable of dye adsorption, and a metal oxide layer capable of adsorbing dye in the form of nanotubes on the porous layer. The paste of titanium dioxide nanoparticles is coated by a doctor blade method to have a porous layer thickness of 6 μm, the metal oxide layer thickness of the nanotubes is 8-15 μm, and the metal oxides of the nanotube type are The pore size is 10-500 nm in diameter, and the nanotubes are TiO ₂ nanotubes, 0.25 mm thick, ultrasonically washed with 99.6% pure Ti foil in distilled water and acetone, and then 60% HCLO4, butanol and ethanol in volume ratios. Dip into a mixed solution mixed with 1: 6: 9, apply electrolytic polishing by applying a voltage of 20V at -20 ° C for 5 minutes, wash with distilled water, and then wash with 0.38wt% NH ₄ F and 1.79wt It was immersed in C ₂ H ₆ O ₂ solution containing% H ₂ O and subjected to primary oxidation by applying a voltage of 70 V for 6 to 10 hours, and washed and sintered at 480 ° C. for 30 minutes to crystallize, 0.38 wt% NH ₄ F And 1.79wt% H ₂ O in a C ₂ H ₆ O ₂ solution containing a dye applied for 10 minutes at 20 ℃ to apply a voltage of 10V secondary oxidation and soaked in 10% hydrogen peroxide for 24 hours and separated Photoelectrode for sensitized solar cell delete delete delete delete

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