KR20160060602A - Method for manufacturing electrodes for use in dye-sensitized solar cells - Google Patents

Abstract

A method of manufacturing an electrode for a dye-sensitized solar cell comprising the steps of: forming an oxide semiconductor porous film on a substrate to produce an electrode substrate; and immersing the electrode substrate in a sensitizing dye solution to adsorb the sensitizing dye on the oxide semiconductor porous film Wherein the electrode substrate is immersed in the sensitizing dye solution in a state in which the electrode substrate is laminated so as to form a plurality of layers without contacting each other in the step of adsorbing the sensitizing dye. .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for manufacturing a dye-sensitized solar cell,

The present invention relates to a method of manufacturing an electrode for a dye-sensitized solar cell.

The present application claims priority based on Japanese Patent Application No. 2013-196003 filed on September 20, 2013, the contents of which are incorporated herein by reference.

Conventionally, as a method of adsorbing the sensitizing dye to the oxide semiconductor porous film in the production of a semiconductor electrode for a dye-sensitized solar cell, a method of immersing an oxide semiconductor porous film formed on a substrate in a solution containing a sensitizing dye (sensitizing dye solution) (See, for example, Patent Document 1).

As another example of the method of immersing the oxide semiconductor porous film in the sensitizing dye solution, the oxide semiconductor porous film formed on the substrate is placed in contact with the sink (no mass having no perforations) There is disclosed a method of adjusting the degree of adsorption of an increase / decrease dye (increase / decrease of a dye) in an oxide semiconductor porous film by immersing a substrate having an oxide semiconductor porous film formed on the increase / decrease coloring solution in the oxide semiconductor porous film (for example, see Patent Document 1) .

Japanese Patent Application Laid-Open No. 2004-335366 Japanese Patent Application Laid-Open No. 2013-157223

In the method of Patent Document 1, efficiency is poor because basically one substrate can be treated with one container. On the other hand, if efficiency is aimed by merely overlapping a plurality of substrates, the adsorption of the sensitizing dye There was a problem that it became uneven. If the adsorption of the sensitizing dye is not uniform, the performance of the dye-sensitized solar cell is lowered or deviated.

In the method of Patent Document 2, adsorption of the increasing and decreasing dye is unintentionally intentionally aimed at the design effect. However, this is not preferable from the viewpoint of the performance of the dye-sensitized solar cell and the manufacturing efficiency has not been improved.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method of manufacturing an electrode for a dye-sensitized solar cell capable of uniformly adsorbing an increase / decrease dye even in a long oxide semiconductor porous film.

[1] A process for producing an electrode substrate, comprising the steps of: forming an oxide semiconductor porous film on a substrate to produce an electrode substrate;

And a step of immersing the electrode substrate in a sensitizing dye solution to adsorb the sensitizing dye to the oxide semiconductor porous film,

Wherein the electrode substrate is immersed in the sensitizing dye solution in a state in which the electrode substrate is laminated so as to form a plurality of layers without contacting each other in the step of adsorbing the sensitizing dye.

[2] In the step of adsorbing the sensitizing dye, the electrode substrate is laminated so as to form a plurality of layers without contacting each other via the separator, and the sensitizing dye solution can be brought into contact with the electrode substrate Wherein the electrode for a dye-sensitized solar cell according to the above-mentioned [1]

[3] The separator according to any one of [1] to [4], wherein the separator has at least one structure selected from the group consisting of a structure in which the enhancement / enhancement dye solution permeates the separator and a structure in which a space is formed between the separator and the electrode substrate to permeate the enhancement / (2). The method for producing an electrode for a dye-sensitized solar cell according to the above (2)

[4] The method for manufacturing an electrode for a dye-sensitized solar cell according to [3], wherein the separator is composed of at least one member selected from the group consisting of a sheet, a linear member and a granular material.

[5] The method for producing an electrode for a dye-sensitized solar cell according to [2], wherein the separator is a sheet having an uneven surface.

[6] The method for manufacturing an electrode for a dye-sensitized solar cell according to [2], wherein the separator is a sheet having at least one through-hole.

[7] The method for producing an electrode for a dye-sensitized solar cell according to [2], wherein the sheet is a nonwoven fabric containing a solvent-resistant resin.

[8] In the step of adsorbing the sensitizing dye, the electrode substrate is held in contact with the edge of the electrode substrate so that the electrode substrate is in contact with each other so as to form a plurality of layers. A method for manufacturing a battery electrode.

[9] An electrode for a dye-sensitized solar cell produced by the method described in [1] above.

According to the present invention, in the step of adsorbing the sensitizing dye to the oxide semiconductor porous film, the electrode substrate is immersed in the sensitizing dye solution so as to form a plurality of layers without contact with each other. For example, , A space is appropriately formed between the electrode substrates, and the increase / decrease dye solution penetrates into the gap. Therefore, the increase and decrease color can be adsorbed uniformly on the oxide semiconductor porous film without speckling efficiently.

1 is a schematic diagram showing a step of a method for manufacturing an electrode for a dye-sensitized solar cell according to this embodiment.
Fig. 2 is a schematic diagram showing one step of a method for producing an electrode for a dye-sensitized solar cell according to the present embodiment.
3 is a schematic diagram showing one step of a method for manufacturing an electrode for a dye-sensitized solar cell according to this embodiment.
4 is a schematic diagram showing one step of a method for manufacturing an electrode for a dye-sensitized solar cell according to the present embodiment.
5 is a schematic diagram showing one step of a method for manufacturing an electrode for a dye-sensitized solar cell according to the present embodiment.
6 is a schematic diagram showing one step of a method for manufacturing an electrode for a dye-sensitized solar cell according to the present embodiment.

An embodiment of a method for producing an electrode for a dye-sensitized solar cell of the present invention will be described.

The present invention is not intended to be limited to the details of the present invention unless specifically stated otherwise.

≪ Method of manufacturing electrode for dye-sensitized solar cell >

A method of manufacturing an electrode for a dye-sensitized solar cell in accordance with an embodiment of the present invention includes the steps of: forming an electrode substrate by forming an oxide semiconductor porous film on a substrate; dipping the electrode substrate in a sensitizing dye solution to form an oxide semiconductor porous film; And then adsorbing it.

Further, each of the above steps is performed in the order described.

The method for forming the oxide semiconductor porous film in the step of forming the electrode substrate is not particularly limited. For example, a method of forming a metal film on a transparent conductive film (or a conductive layer such as a metal mesh) A method of applying a paste containing oxide particles by a printing method, a method of spraying metal oxide particles on a transparent conductive film formed on a substrate constituting a semiconductor electrode, and the like. In the case of using a transparent conductive film or a conductive layer such as a metal mesh for the opposite electrode, the conductive film formed on the substrate constituting the semiconductor electrode does not necessarily have to be transparent.

1, a substrate 11, a transparent conductive film 12 formed on the substrate 11, and an oxide semiconductor porous film (not shown) stacked on the transparent conductive film 12 13) is obtained. Here, the thicknesses of the substrate 11, the transparent conductive film 12, and the oxide semiconductor porous film 13 are not particularly limited and can be the same as in the conventional art. For example, the thickness of the base material 11 is preferably 8 to 500 탆, more preferably 20 to 300 탆, and even more preferably 50 to 200 탆. The thickness of the transparent conductive film 12 is preferably 1 nm to 1 탆, more preferably 10 nm to 500 nm, and even more preferably 150 nm to 300 nm. The thickness of the oxide semiconductor porous film 13 is preferably 100 nm to 50 占 퐉, more preferably 1 占 퐉 to 30 占 퐉, and still more preferably 5 占 퐉 to 20 占 퐉.

In the case of forming the oxide semiconductor porous film 13 by the printing method, a paste containing metal oxide particles is coated on the substrate 11 on which the transparent conductive film 12 is formed to form a coating film on the transparent conductive film 12 The coating film is baked at a temperature not higher than the temperature at which the base material 11 is not deteriorated to form the oxide semiconductor porous film 13. [ The temperature below the temperature at which the substrate 11 does not deteriorate is a temperature of 150 DEG C or lower when the substrate 11 is a transparent substrate made of plastic. The lower limit of the firing temperature is not particularly limited as long as a desired firing effect can be achieved, but it is preferably at least 50 占 폚.

Known methods for spraying metal oxide particles (hereinafter abbreviated as " spraying method ") are used. For example, spraying, cold spraying, aerosol deposition (hereinafter abbreviated as "AD method" ) And the like.

The spraying method is a method in which the sprayed material (metal oxide particles in the present embodiment) is heated and sprayed onto the base material 11 on which the transparent conductive film 12 is formed to form a thin film on the substrate 11 on which the transparent conductive film 12 is formed (In this embodiment, the oxide semiconductor porous film 13). As a heat source for heating the thermal sprayed material, a combustion salt or plasma is used, and the thermal sprayed material in the form of droplets or fine particles is jetted to the substrate 11 on which the transparent conductive film 12 is formed by a high-speed gas flow or the like. A sprayed material in a droplet shape or a fine particle form solidifies on the base material 11 on which the transparent conductive film 12 is formed and is closely contacted to form a thin film.

The cold spray method is a method in which a powder material (metal oxide particles in this embodiment) is collided with a substrate in a solid state at a melting temperature or less to form a thin film (in this embodiment, Oxide semiconductor porous film 13).

The AD method is a method in which raw material particles (metal oxide particles in the present embodiment) are accelerated to a subsonic or supersonic speed by a carrier gas containing an inert gas such as helium, argon or nitrogen to form a transparent conductive film 12 The raw material particles are jetted to the base material 11 at a high speed to bond the raw material particles and the base material 11 on which the transparent conductive film 12 is formed or the raw material particles to each other to bond the raw material particles on the base material 11 on which the transparent conductive film 12 is formed Is a technique for forming a thin film.

At least a part of the raw material particles colliding with the surface of the base material 11 on which the transparent conductive film 12 is formed are eaten by the surface of the base material 11 on which the transparent conductive film 12 is formed, State. Further, by continuing the spraying, separate fine particles collide with the raw material particles ingested into the surface of the base material 11 on which the transparent conductive film 12 is formed, and the raw material particles collide with each other, The raw material particles are bonded to each other mainly on this new surface. In the collision between the raw material particles, since the temperature rise at which the raw material particles are melted hardly occurs, there is substantially no grain boundary layer including glassy matter at the interface between the raw material particles. By continuing the spraying of the raw material particles, a plurality of raw material grains are bonded to the surface of the base material 11 on which the transparent conductive film 12 is formed gradually to form a dense thin film. Since the formed thin film has sufficient strength, vitrification by firing is unnecessary.

As the AD method, for example, ultra-fine particle beam deposition method disclosed in International Publication WO01 / 27348A1 pamphlet, and brittle material ultrafine particle low temperature forming method disclosed in Japanese Patent No. 3265481 are used.

In these known AD methods, it is important to preliminarily spray raw material particles to be sprayed with a ball mill or the like so that internal strain to the extent that cracks will occur is added to raw material particles in advance. By applying this internal deformation, the sprayed fine particles can easily cause fracture or deformation when they collide with the base material 11 or the already deposited raw material particles, so that a dense film can be formed as a result.

In the present embodiment, it is not always necessary to apply internal deformation to the raw material particles in advance.

In the present embodiment, it is preferable that the spraying of the raw material particles is performed in a room temperature environment.

Here, the room temperature means a temperature sufficiently lower than the melting point of the raw material particles, and is substantially 200 DEG C or less.

The temperature of the room temperature environment is preferably not higher than the melting point of the base material (11). Particularly, when the substrate 11 is made of a resin, it is preferable that the temperature of the room temperature environment is lower than the glass transition temperature of the substrate 11.

The material of the base material 11 constituting the electrode substrate 10 is not particularly limited and may be glass, resin, or metal.

As the glass, those having transparency to visible light are preferable, and examples thereof include soda lime glass, quartz glass, borosilicate glass, bicycle glass, alkali-free glass, cheeseclass glass, white plate glass and the like.

As the resin (plastic), those having transparency to visible light are preferable, and examples thereof include polyacryl, polycarbonate, polyester, polyimide, polystyrene, polyvinyl chloride, polyamide and the like. Of these, polyesters, particularly polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), are produced and used in large quantities as transparent heat-resistant films, which is preferable from the viewpoint of availability.

From the viewpoint of producing a thin, light and flexible dye-sensitized solar cell, the substrate 11 is preferably a transparent substrate made of plastic, and from this point of view, it is preferable that the substrate 11 is a PET film or a PEN film.

The transparent conductive film 12 is not particularly limited, but a transparent conductive film used in a conventionally known dye-sensitized solar cell can be applied. For example, a thin film made of a metal oxide or a metal thin film processed into a mesh- .

Examples of the metal oxide include indium oxide / tin oxide (ITO), fluorine doped tin oxide (FTO), zinc oxide, tin oxide, antimony doped tin oxide (ATO), indium oxide / zinc oxide (IZO) GZO), titanium oxide, and the like. Of these, ITO having a small specific resistance and high electrical conductivity and FTO having excellent heat resistance and weather resistance are particularly preferable.

As the material of the metal thin film processed into a mesh, there may be mentioned metals such as titanium, platinum, gold, silver, copper, chromium, nickel, tungsten, iron and aluminum or alloys of two or more of these metals. It is not limited.

Next, the step of adsorbing the sensitizing dye to the oxide semiconductor porous film 13 will be described.

Here, a long electrode substrate 10 is wound in a roll shape and immersed in a solution of a sensitizing dye.

In the step of adsorbing the sensitizing dye to the oxide semiconductor porous film 13, first, as shown in Figs. 2 and 3, the separator 20 is placed on the oxide semiconductor porous film 13 of the electrode substrate 10 do.

Subsequently, as shown in Figs. 4 and 5, the electrode substrate 10 in a state in which the separator 20 is laminated is rolled. As a result, the electrode base materials 10 do not contact with each other but overlap each other so as to form a plurality of layers at intervals. That is, the separator 20 functions as a spacer that separates the electrode substrate 10 from each other.

The separator 20 is not particularly limited as long as it can overlap the electrode substrates 10 so that the electrode substrate 10 does not contact each other and the sensitizing dye solution can contact the electrode substrate 10 .

For example, the method of the present invention can be carried out by using a planar non-porous sheet-like separator 20 to form a gap through which the increase / decrease dye solution penetrates between the electrode substrates 10. This can be performed by, for example, loosely winding the separator 20 and the electrode substrate 10 so as to form a gap between the separator 20 and the electrode substrate 10 when the electrode substrate 10 is wound with the separator 20 interposed therebetween.

The separator 20 has a structure in which the enhancement / enhancement dye solution permeates the separator 20 and a structure for forming a space for permeating the enhancement / enhancement dye solution between the separator 20 and the electrode substrate 10 It is preferable to have at least one structure selected from the group consisting of With this structure, even when the electrode substrate 10 and the separator 20 are brought into close contact with each other, the sensitizing dye solution can be brought into contact with the electrode substrate 10.

Regarding the shape of the separator 20, it is preferable that the separator 20 is composed of at least one member selected from the group consisting of a sheet, a linear member and a granular substance.

As an example of the sheet-like separator 20, the surface of the separator 20 may be non-flat. A sheet having no surface is a sheet on which surface convexity or concavity and convexity are present and whose surface is not smooth. Here, the height of the convex portion is not particularly limited. For example, the distance between the bottom of the concave portion in the flat portion or the concave-convex portion of the sheet surface and the electrode substrate 10 is preferably 1 to 10 mm, More preferably 5 占 퐉 to 1 mm, and particularly preferably 10 占 퐉 to 500 占 퐉. A minute gap is formed between the sheet (separator 20) whose surface is not smooth and the electrode substrate 10 where the surface is not smooth and the sheet whose surface is not smooth (separator 20) . Therefore, the increase / decrease dye solution permeates between the separator 20 and the electrode base material 10, and as a result, the increase / decrease dye solution permeates between the electrode base materials 10.

Another example of the sheet-like separator 20 is a sheet having at least one through hole. The shape, size and number of the through holes are not particularly limited as long as they can prevent the electrode substrate 10 from contacting each other and allow the increase / decrease dye solution to pass therethrough. Examples of the shape of the through hole include a circle, an ellipse, a square, a triangle, a star, and the like, and through holes of different shapes may be formed. Although the number of the through holes is preferably two or more, the specific number, shape, and size of the through holes may be appropriately adjusted so as to become the later-described porosity. The sheet-like separator 20 having a through hole has a frame-like shape in which only the outer edge of the electrode substrate 10 is in contact with the outer edge of the electrode substrate 10, (Frame portion) having a plurality of small through holes is also included.

The sheet-like separator 20 may have a clip structure formed by bending a metal plate or a resin plate (for example, a double clip). In this case, the method of the present invention can be carried out by sandwiching the electrode substrate 10 with a clip. The sheet-like separator 20 can be formed by a method of forming the separator 20 on the electrode substrate 10 using a photoresist or a method of forming an adhesive tape of a material resistant to a solvent used for a sensitizing dye solution, They may be laminated on the electrode substrate 10 by a method of attaching them on the substrate 10 at regular intervals.

In the case where the separator 20 is a frame-like base material, it is preferable that the electrode base materials 10 are formed in such a manner that the electrode base materials 10 do not come in contact with each other at a portion not contacting the separator 20 , The size of the opening, the size of the width of the frame, and the like are set.

It is also one of the preferred embodiments of the present invention to use, as the separator 20, a sheet having a non-flat surface and at least one through hole.

When the separator 20 is a sheet-like sheet having a through-hole, it is preferable that the separator 20 has a plurality of through-holes all over the whole (entire region) of the sheet facing at least the electrode substrate 10. As such a sheet, for example, a sheet of a mesh-like (network) type can be mentioned.

When the separator 20 is a frame-like base material, it is preferable that the separator 20 has a plurality of through holes all over the whole (entire region) of the frame portion. As a frame-like base material having a plurality of through holes in the frame portion, for example, a mesh-like (network-like) base material formed in a frame shape can be cited.

The porosity of the separator 20, that is, the ratio of the through hole in the separator 20 is preferably 50 to 95% by volume, more preferably 60 to 80% by volume.

If the porosity of the separator 20 is equal to or lower than the lower limit of the above range, the increase / decrease color can be uniformly adsorbed to the oxide semiconductor porous film 13 through the through hole of the separator 20 without spots. On the other hand, when the porosity of the separator 20 is not more than the upper limit of the above range, the electrode substrate 10 is not brought into contact with each other when the electrode substrate 10 is rolled up with the separator 20 interposed therebetween.

When the separator 20 is a linear member, its shape, size, and number are not particularly limited as long as it can prevent contact between the electrode substrate 10 and allow the increase / decrease dye solution to pass therethrough. As the specific shape of the line-shaped separator 20, a fiber shape, a wire shape, and a rod shape can be mentioned. The cross-sectional shape of the separator 20 can be any shape selected from a circle, an ellipse, a square, a triangle, a molding, And may be extended or curved. Further, a method of disposing one or two or more wires in a waveform reciprocating in the longitudinal direction or the width direction of the electrode substrate 10, or a method in which a plurality of film objects are arranged side by side in the longitudinal direction or width direction of the electrode substrate 10 The separator 20 may be formed.

The line-shaped separator 20 may have a clip structure (e.g., a gem clip) in which the wire is bent into a long and long spiral shape. In this case, the method of the present invention can be carried out by sandwiching the electrode substrate 10 with a clip. In addition, the above-mentioned linear water may be porous or non-porous.

The shape, size, and number of the separator 20 are not particularly limited as long as they can prevent the electrode substrate 10 from contacting each other and allow the increase / decrease dye solution to pass therethrough. Examples of the shape of the granular material include spheres, cylinders, cubes, and rectangular parallelepipeds. More specific examples of the particulate material include glass beads, silica particles, resin particles (for example, "Micropearl" manufactured by Sekisui Chemical Co., Ltd.) and metal particles.

In addition, the particulate material may be porous or non-porous.

Since the separator 20 is immersed in the sensitizing dye solution together with the electrode substrate 10, it is preferable that the separator 20 contains a solvent-resistant material. The solvent-resistant material referred to herein is a material excellent in resistance to a solvent used in a sensitizing dye solution.

Examples of the material for solvent resistance include a solvent-resistant metal such as stainless steel, a solvent-resistant resin such as polyolefin, vinylon, and polyester, natural fibers such as cotton, hemp, dog, paper and the like.

The properties of the material constituting the separator 20 are not particularly limited as long as the separator 20 can function as a separator as described above. The material may be a solid as well as a gel.

The separator 20 may be laminated on the electrode substrate 10 in advance, or may be formed by coating a liquid or gel-like substance on the electrode substrate 10 in the form of a film, a dot or a film, and then curing .

The thickness of the separator 20 is preferably 10 占 퐉 to 100 占 퐉.

When the thickness of the separator 20 is equal to or smaller than the lower limit of the above range, contact between the electrode substrates 10 can be reliably prevented when the electrode substrate 10 is rolled up via the separator 20. On the other hand, if the thickness of the separator 20 is not more than the upper limit of the above range, the separator 20 is not too thick, so that the electrode substrate 10 in a state in which the separator 20 is laminated can be rolled.

As the separator 20, it is possible to easily roll the electrode substrate 10 in the form of a roll while the electrode substrate 10 is laminated on the electrode substrate 10, A mesh-like sheet is preferable because the solution of the sensitizing dye can easily penetrate between the two. Preferable examples of the mesh-like sheet include a nonwoven fabric containing the resin.

Subsequently, as shown in Fig. 6, the electrode substrate 10 in a rolled state is immersed in the sensitizing dye solution 40 in the solution tank 30 via the separator 20, Whereby the sensitizing dye is adsorbed to the porous film 13.

When the electrode substrate 10 in a rolled state is immersed in the sensitizing dye solution 40, the temperature of the sensitizing dye solution 40 is preferably 20 to 80 占 폚, more preferably 30 to 60 占 폚 Do.

If the temperature of the enhancement / enhancement dye solution 40 is not lower than the lower limit of the above range, the enhancement dye contained in the enhancement / enhancement dye solution 40 is easily diffused into the oxide semiconductor porous film 13, 13), the sensitizing dye can be uniformly adsorbed without staining. On the other hand, if the temperature of the enhancement / enhancement dye solution 40 is not more than the upper limit of the above range, the volatilization of the solvent constituting the enhancement / enhancement dye solution 40 can be suppressed and the substrate 11 constituting the electrode base 10 As a result, the sensitizing dye can be uniformly adsorbed to the oxide semiconductor porous film 13 without staining.

When the electrode substrate 10 in a rolled state is immersed in the sensitizing dye solution 40, it is preferable to stir the sensitizing dye solution 40 using an agitating device. As the stirring apparatus, a magnetic stirring rod or a stirring blade is used.

As described above, when the electrode substrate 10 in a rolled state is immersed in the sensitizing dye solution 40, the sensitizing dye solution 40 is agitated so that the sensitizing dye solution 40 is uniformly sensitized to the sensitizing dye solution 40 As a result, it is possible to uniformly adsorb the sensitizing dye to the oxide semiconductor porous film 13 without unevenness.

The concentration of the enhancement / enhancement dye solution 40 is preferably 0.1 mM to 10 mM, more preferably 0.1 mM to 5 mM, and the gene in yeast is particularly preferable.

If the concentration of the enhancement / enhancement dye solution 40 is equal to or more than the lower limit value and the upper limit value of the above range, the enhancement / enhancement dye contained in the enhancement / enhancement dye solution 40 is easily diffused into the oxide semiconductor porous film 13, The sensitizing dye can be uniformly adsorbed on the porous film 13 without staining.

Examples of the sensitizing dye contained in the sensitizing dye solution 40 include organic dyes such as ruthenium complex, cyanine and chlorophyll. A ruthenium complex is suitable as the sensitizing dye because it has a wide wavelength region to be absorbed and a long lifetime of the photoexcitation, so that electrons transferred to the oxide semiconductor porous film 13 are stabilized. Examples of ruthenium complexes include cis-di (thiocyanato) -bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II), cis- Tetrabutylammonium salt of bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) (hereinafter referred to as N719).

As the solvent constituting the enhancement / enhancement dye solution 40, for example, alcohols can be mentioned, but the solvent is not particularly limited. As the alcohol, the skeleton of the chemical structure thereof may be linear, branched or cyclic, and may be any of monohydric alcohols and polyhydric alcohols, and examples thereof include methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-methyl-1-propanol (isobutanol), 2-butanol, 2-methyl-2-propanol (tert-butanol) and ethylene glycol.

In the step of drying the electrode substrate 10, it is preferable that the temperature for drying the electrode substrate 10 is a temperature equal to or lower than a temperature at which the substrate 11 is not deteriorated. The temperature below the temperature at which the substrate 11 does not deteriorate is a temperature of 150 DEG C or lower when the substrate 11 is a transparent substrate made of plastic. The lower limit of the drying temperature is not particularly limited as long as it can sufficiently dry the electrode substrate 10, but is preferably 50 占 폚 or higher. However, in the case of blow drying, it may be carried out at room temperature (about 20 to 30 캜).

In the step of drying the electrode substrate 10, after the electrode substrate 10 on which the sensitizing dye has been adsorbed to the oxide semiconductor porous film 13 is removed from the sensitizing dye solution 40, the electrode substrate 10 and the separator (20). After separating the electrode substrate 10 and the separator 20, the electrode substrate 10 is dried.

Through this drying step, a substrate 11, a transparent conductive film 12 formed on one surface of the substrate 11, an oxide semiconductor porous film 13 laminated on the transparent conductive film 12, Thereby obtaining a semiconductor electrode for a dye-sensitized solar cell having a sensitizing dye adsorbed on the porous film (13).

According to the method for manufacturing an electrode for a dye-sensitized solar cell of the present embodiment, in the step of adsorbing a sensitizing dye to the oxide semiconductor porous film 13, the electrode substrate 20 is contacted with the electrode substrate 20 via the separator 20 A gap is appropriately formed between the electrode base materials 10 even when the electrode base material 20 is wound in the form of a roll, And the increase / decrease dye solution penetrates into the gap. Therefore, the increase and decrease dye can be adsorbed uniformly on the oxide semiconductor porous film 13 without staining. In addition, even in the state where the electrode substrate 20 is wound in the form of a roll, since the coloring matter can be uniformly adsorbed to the oxide semiconductor porous film 13 without any unevenness, The sensitizing dye can be adsorbed to the oxide semiconductor porous film 13 of the oxide semiconductor porous film.

After the adsorption of the sensitizing dye to the oxide semiconductor porous film 13 is completed, the separator 20 is separated from the electrode substrate 10 and the separator 20 is washed with a solvent such as the above-mentioned alcohol, In the step of adsorbing the sensitizing dye to the oxide semiconductor porous film, the separator 20 can be reused. The separator 20 is excellent in resistance to the solvent used for the sensitizing dye solution and the separator 20 does not need to exert excessive pressure when adsorbing the sensitizing dye to the oxide semiconductor porous film 13, It can be reused because it is hard to cause deformation or corrosion.

In the present embodiment, the electrode substrate 10 is immersed in the sensitizing dye solution 40 in the state that the electrode substrate 10 is rolled up with the separator 20 interposed therebetween to form an oxide semiconductor porous film 13) is adsorbed on the surface of the support, but the present embodiment is not limited to this. In this embodiment, the electrode base material 10 on the sheet on which the oxide semiconductor porous film 13 is formed may be immersed in the increase / decrease dye solution 40 in a state where a plurality of the electrode base materials 10 are stacked with the separator 20 interposed therebetween. In this way, the same effect as described above can be obtained.

In addition, the method of the present invention may be carried out by overlapping the surfaces of the electrode substrate on which the oxide semiconductor porous film is not formed, and overlapping the electrode substrate so that the surfaces on which the oxide semiconductor porous film is formed are not in contact with each other.

≪ Preparation method of dye-sensitized solar cell >

A dye-sensitized solar cell can be manufactured by a known method using an electrode for a dye-sensitized solar cell manufactured by the above-described method. Examples of the method for producing a dye-sensitized solar cell include (1) a step of producing a semiconductor electrode (a step of producing a semiconductor electrode) by the method for producing an electrode for a dye-sensitized solar cell according to the above- (3) a step of disposing a sealing material so as to surround the electrolyte layer, and bonding the semiconductor electrode and the counter electrode via the sealing material to the electrolyte electrode layer Method. Here, steps (2) and (3) may be performed in reverse order. Hereinafter, each step will be described in detail.

A counter electrode is formed separately from the semiconductor electrode.

A transparent conductive film containing ITO, zinc oxide, platinum or the like is formed on the same substrate as the semiconductor electrode by sputtering, printing, spraying, or the like. However, this conductive film is not necessarily transparent when the conductive film formed on the substrate constituting the semiconductor electrode is transparent.

Further, a carbon paste or the like is formed on the surface of the transparent conductive film (opposite to the surface in contact with the substrate in the transparent conductive film) to form a catalyst layer.

Subsequently, an electrolytic solution is applied to the oxide semiconductor porous film of the semiconductor electrode by a casting method, a coating method, a dipping method or the like to form an electrolyte layer (step (2)).

After the sealing material is disposed to surround the formed electrolyte layer, the semiconductor electrode and the opposing electrode are disposed to face each other, and the outer peripheral portion of each electrode is sealed with the sealing material interposed therebetween to seal the semiconductor electrode and the opposing electrode (Step (3) .

As described above, the dye-sensitized solar cell in which the semiconductor electrode and the counter electrode are adhered to each other with the sealing material interposed therebetween with a predetermined gap therebetween, and the gap between the electrodes is filled with the electrolytic solution is obtained.

Next, an example of the case of reversing the order of the steps (2) and (3) will be described.

After formation of the catalyst layer, an uncured sealing material is disposed on the outer peripheral portion of the surface of the semiconductor electrode opposite to the opposing electrode in a frame shape having a predetermined width dimension, and the sealing material surrounds the oxide semiconductor porous film.

Next, the semiconductor electrode and the counter electrode are disposed to face each other, and the peripheral portion of each electrode is bonded via the sealing material to seal the semiconductor electrode and the counter electrode.

Then, the sealing material is cured by heating, ultraviolet irradiation, or the like, thereby bonding the semiconductor electrode and the counter electrode.

Subsequently, a liquid injection hole reaching the gap (inner space) between the semiconductor electrode and the counter electrode is formed from the outside by, for example, pulling out the liquid injection hole forming member protruding from the outer peripheral wall portion of the substrate of the counter electrode in advance.

Subsequently, the junction body formed by bonding the semiconductor electrode and the counter electrode is placed under a reduced-pressure atmosphere, and the liquid injection hole is immersed in a container (not shown) holding the electrolyte solution. Inject.

After the electrolyte is injected, the inlet is closed with an adhesive or the like to seal the inner space.

As described above, the dye-sensitized solar cell is obtained in which the semiconductor electrode and the counter electrode are disposed opposite to each other with a predetermined interval therebetween through the sealing material, and the gap between the electrodes is filled with the electrolytic solution.

As the material of the sealing material, a resin material or the like which can be softened or fluidized under a certain condition and solidified by a suitable treatment, such as a resin composition containing a thermoplastic resin, an ultraviolet curable resin, a thermosetting resin, an ultraviolet curable resin and a thermosetting resin Can be used.

As the electrolytic solution, an electrolytic solution used as a conventionally known dye-sensitized solar cell can be applied.

As the electrolytic solution of the dye-sensitized solar cell, it is generally used that a redox pair (electrolyte) is dissolved in a solvent.

An organic solvent may be used as a component of the electrolytic solution. Examples of the organic solvent include alcohols, nitriles, ethers, esters, ketones, hydrocarbons, halogenated hydrocarbons and the like.

As the alcohol, the skeleton of the chemical structure thereof may be linear, branched or cyclic, and may be any of monohydric alcohols and polyhydric alcohols. Examples of the alcohol include methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-methyl-1-propanol (isobutanol), 2-butanol, 2-methyl-2-propanol (tert-butanol) and ethylene glycol.

Examples of the nitriles include acetonitrile and propionitrile.

As the ether, the skeleton of the chemical structure thereof may be linear, branched or cyclic, and examples thereof include dimethyl ether, diethyl ether, ethyl methyl ether, tetrahydrofuran and the like.

Examples of the esters include ethyl acetate, propyl acetate, butyl acetate and the like.

Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and γ-butyrolactone.

As the hydrocarbon, the skeleton of the chemical structure thereof may be linear, branched or cyclic, and may be any of an aliphatic hydrocarbon and an aromatic hydrocarbon, and examples thereof include pentane, hexane, heptane, octane, Hexane, toluene, xylene, and the like.

Examples of the halogenated hydrocarbons include methylene chloride and chloroform.

As the redox pair (electrolyte) dissolved in the electrolytic solution, conventionally known redox pairs can be applied.

Examples of the redox pair include a combination of an iodine molecule and iodide or a combination of a bromine molecule and a bromine compound.

Examples of the iodide include metal iodides such as sodium iodide (NaI) and potassium iodide (KI), iodides such as tetraalkylammonium iodide, pyridinium iodide, and imidazolium iodide. have.

Examples of the bromine compound include metal bromides such as sodium bromide (NaBr) and potassium bromide (KBr), and bromine salts such as tetraalkylammonium bromide, pyridinium bromide and imidazolium bromide.

According to the method for producing a dye-sensitized photovoltaic cell of the present embodiment, since the semiconductor electrode obtained by carrying out a process requiring a long time to adsorb the sensitizing dye to the oxide semiconductor porous film in a separate step is used, It is possible to continuously produce dye-sensitized solar cells by carrying out various treatments (joining with counter electrodes, injecting electrolyte, and the like) while carrying them on a roll-to-roll basis . That is, by performing the step of adsorbing the sensitizing dye to the oxide semiconductor porous film by a separate step, the production efficiency can be improved.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[Experimental Example]

An ITO-PEN film (thickness: 125 m, width 10 cm x length 30 cm, trade name: CX13G-125N-U2, manufactured by Oike Kogyo Co., Ltd.) having ITO as a transparent conductive layer was formed on the transparent conductive layer A titanium oxide film having a thickness of 10 占 퐉 was formed by a coating method using a titanium oxide paste (trade name: Ti-Nanoxide DL, manufactured by Solaronix Co., Ltd.), followed by baking at 120 占 폚 for 30 minutes to form a titanium oxide porous film To obtain an electrode substrate.

Subsequently, a nonwoven fabric (porosity of 75 vol%, thickness of 30 m, width of 10 cm x length of 30 cm, trade name: HOP-15, manufactured by Hirose Seisakusho) containing polyolefin resin was applied to the titanium oxide porous film formed of ITO- And then one end of the electrode substrate was fixed with a nonwoven fabric by Capton Tape in a polypropylene tube having a diameter of 70 mm and the nonwoven fabric and the electrode substrate were rolled into a polypropylene tube After winding, the other end of the electrode substrate was fixed to the polypropylene tub by a capstan tape again. As a result, the electrode substrate was rolled in a polypropylene tub through a nonwoven fabric.

Subsequently, an N719 dye solution in which the dye N719 was dissolved in a mixed solvent of acetonitrile / tert-butanol (1/1, volume ratio) so as to have a concentration of 0.3 mM was prepared. To this N719 dye solution, Shaped electrode substrate was immersed at 30 DEG C for 16 hours.

After that, the electrode substrate was taken out from the N719 dye solution, the electrode substrate and the nonwoven fabric were separated, and the electrode substrate was dried with nitrogen gas to obtain a semiconductor electrode.

The dye adsorption density of the semiconductor electrode was measured in order to quantitatively evaluate the amount of N719 dye adsorbed on the titanium oxide porous film.

Five regions (regions) were cut out from a semiconductor electrode having a length of 30 cm in a width of 5 cm along the longitudinal direction thereof to prepare five samples for measuring dye adsorption density. Each of the samples for measuring five dye adsorption densities was immersed in a potassium hydroxide (KOH) solution, and the dye adsorption density was measured for each sample.

At this time, the dye absorption density was measured with the molar extinction coefficient of the dye N719 being 14200 (wavelength = 538 nm).

As a result, the dye adsorption density was 0.6 ± 0.05 (10 ^-8 mol / ㎠ · ㎛) as a sample for measuring all dye adsorption densities. When the obtained semiconductor electrode was observed with naked eyes, it was confirmed that the dye was uniformly adsorbed throughout the entire surface without color unevenness.

[Reference Example]

The electrode substrate was immersed in the N719 dye solution at 30 DEG C for 16 hours in the same manner as in the Example except that the nonwoven fabric was not used and the electrode substrate was not detected in a roll of polypropylene.

The dye adsorption density of the semiconductor electrode of the electrode substrate was measured in the same manner as in the examples.

As a result, it was confirmed that the dye adsorption density was 0.6 +/- 0.05 (10 ^-8 mol / cm < 2 > This means that, even in the case where the nonwoven fabric is interposed in the above embodiment, it was possible to adsorb an amount of dye equivalent to that in the case where the nonwoven fabric was not used.

10: Electrode substrate
11: substrate
12: transparent conductive film
13: oxide semiconductor porous film
20: Separator
30: Solution tank
40: Additive dye solution

Claims (9)

A step of forming an oxide semiconductor porous film on a substrate to produce an electrode substrate,
And a step of immersing the electrode substrate in a sensitizing dye solution to adsorb the sensitizing dye to the oxide semiconductor porous film,
Wherein the electrode substrate is immersed in the sensitizing dye solution in a state in which the electrode substrate is laminated so as to form a plurality of layers without contacting each other in the step of adsorbing the sensitizing dye. The method according to claim 1, wherein in the step of adsorbing the sensitizing dye, the electrode substrate is laminated so as to form a plurality of layers without contacting each other via a separator and the sensitizing dye solution can contact the electrode substrate By weight based on the total weight of the dye-sensitized solar cell. The separator according to claim 2, wherein the separator comprises at least one member selected from the group consisting of a structure through which the enhancement / enhancement dye solution permeates the separator and a structure that forms a space for permeating the increase / decrease dye solution between the separator and the electrode base Wherein the electrode for a dye-sensitized solar cell has a structure represented by the following formula: The method for manufacturing an electrode for a dye-sensitized solar cell according to claim 3, wherein the separator is composed of at least one member selected from the group consisting of a sheet, a linear member and a granular material. The method according to claim 2, wherein the separator is a sheet having an uneven surface. The method according to claim 2, wherein the separator is a sheet having at least one through hole. The method for manufacturing an electrode for a dye-sensitized solar cell according to claim 2, wherein the sheet is a non-woven fabric comprising a solvent-resistant resin. 2. The dye-sensitized solar cell according to claim 1, wherein in the step of adsorbing the sensitizing dye, the electrode substrate is held in contact with the electrode substrate so as to be in contact with each other so as to form a plurality of layers, ≪ / RTI > An electrode for a dye-sensitized solar cell, which is produced by the method according to claim 1.

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