JP5599221B2 - Method for forming buffer layer in dye-sensitized solar cell - Google Patents

Description

  The present invention relates to a method for forming a buffer layer in a dye-sensitized solar cell.

Generally, a dye-sensitized solar cell includes a transparent electrode in which a transparent conductive film is formed on a transparent substrate such as a glass plate, a counter electrode in which a transparent conductive film is similarly formed on the surface of the transparent substrate, and these It is composed of an iodine-based electrolyte layer disposed between both electrodes, and a photocatalytic film disposed between the two electrodes and on the surface of the transparent electrode. The photocatalytic film includes titanium oxide (TiO ₂ ) and the like. It is known that after forming a metal oxide, dyeing a photosensitizing dye such as ruthenium.

  According to this configuration, since the transparent electrode and the electrolyte layer are in contact, when liquid is used for the electrolyte, electrons leak from the transparent electrode to the electrolyte layer, and a reverse current is generated. There was a problem that the power generation efficiency decreased.

  As a solution to this problem, the reverse current is prevented by forming a dense film made of a semiconductor such as titanium oxide or zinc oxide between the transparent electrode and the photocatalyst film (metal oxide), a so-called buffer layer. There is a known method (see, for example, Patent Document 1).

JP 2007-31162 A

  By the way, according to the structure of the said patent document 1, when forming a semiconductor film, since it is necessary to sinter at about 500 degreeC high temperature, a lightweight and cheap synthetic resin cannot be used as a board | substrate of a transparent electrode. There was a problem.

Although a method for forming a buffer layer at a low temperature is also disclosed, there is a problem that the apparatus becomes large and expensive because a sputtering method or vacuum deposition is used.
Therefore, an object of the present invention is to provide a method for forming a buffer layer in a dye-sensitized solar cell in which a material that is weak against high temperature such as a synthetic resin can be used as a substrate.

In order to solve the above problems, a method for forming a buffer layer in a dye-sensitized solar cell according to the present invention includes a transparent electrode, a counter electrode, an electrolyte layer disposed between these electrodes, and a transparent electrode between both electrodes. A method of forming a buffer layer disposed between the transparent electrode and the photocatalytic film in a dye-sensitized solar cell comprising a photocatalytic film disposed on the side,
With a precursor of the photocatalyst coating liquid comprising dissolving in an alcohol solution to the surface of the transparent electrode, or after coating, by firing the spray superheated steam, a method of forming a buffer layer.

  In the above formation method, the photocatalyst is titanium oxide, tungsten oxide, tin oxide, zinc oxide, or niobium oxide, and the precursor is the metal alkoxide.

Further, in each of the above forming methods, a spray method, a spin coating method, or a dip method is used when applying the liquid to the surface of the transparent electrode.
Further, in each of the above forming methods, the temperature of the superheated steam is in the range from over 100 ° C. to 300 ° C.
Further, the superheated steam is sprayed in two stages, the temperature of the superheated steam sprayed in the first stage is in the range of over 100 ° C. to 300 ° C., and the temperature range of the superheated steam sprayed in the second stage is 300. In this method, the temperature is in the range of more than 500 ° C up to 500 ° C.

According to the method for forming the buffer layer, when the buffer layer is formed on the transparent electrode, the liquid containing the photocatalyst precursor in the alcohol liquid is applied to the surface of the transparent electrode, or after the application, the superheated steam is applied. Since it is sprayed and fired, that is, it is not necessary to heat the entire electrode, a material with low heat resistance such as a synthetic resin can be used as a substrate material for the transparent electrode, and thus the weight of the solar cell itself is reduced. In addition, the price can be reduced.

  Moreover, the following effects are acquired by spraying the superheated steam from which temperature differs in two steps. That is, by spraying and baking low-temperature superheated steam, hydrolysis and crystallization of titanium oxide are promoted. Thereby, the amount of titanium oxide in the buffer layer increases. And, by spraying high-temperature superheated steam and firing, the generated titanium oxide particles and the bond between the particles and the transparent electrode become strong, and excess water, alcohol, dust, etc. can be removed. .

It is sectional drawing which shows the basic composition of the dye-sensitized solar cell which concerns on embodiment of this invention. It is a side view explaining the formation method of the buffer layer which concerns on Example 1 of this invention. It is an external appearance perspective view of the vapor spray nozzle used for the formation method of the buffer layer based on the Example 1. FIG. It is a side view explaining the formation method of the buffer layer based on Example 2 of this invention. It is a side view explaining the formation method of the buffer layer based on Example 3 of this invention.

Hereinafter, a method for forming a buffer layer in a dye-sensitized solar cell according to an embodiment of the present invention will be described with reference to the drawings.
First, a schematic configuration of the dye-sensitized solar cell according to the present embodiment will be described with reference to FIG.

  As shown in FIG. 1, the dye-sensitized solar cell includes a transparent electrode 1 as a negative electrode, a counter electrode 2 as a positive electrode, an electrolyte layer 3 disposed between the electrodes 1 and 2, and both electrodes 1. , 2 and a photocatalyst film (also a photocatalyst layer) 4 disposed on the transparent electrode 1 side, and a buffer made of titanium oxide, zinc oxide or the like between the transparent electrode 1 and the photocatalyst film 4. Layer 5 is provided to prevent backflow of electrons.

  The transparent electrode 1 is composed of a transparent substrate 11 and a transparent conductive film 12 formed (arranged) on the surface of the transparent substrate 11, and the counter electrode 2 is formed on the surface of the transparent substrate 21 and the transparent substrate 21. The transparent conductive film 22 is formed (arranged).

  As each of the transparent substrates 11 and 21, a synthetic resin plate, a glass plate, or the like is used as appropriate, but a thermoplastic resin such as a polyethylene naphthalate (PEN) film is preferable in terms of weight reduction and price reduction. In addition to polyethylene naphthalate, polyethylene terephthalate, polyester, polycarbonate, polyolefin and the like can also be used.

Further, as the transparent conductive films 12 and 22, tin-added indium oxide (ITO) is preferably used. In addition, fluorine-added tin oxide (FTO), tin oxide (SnO ₂ ), and indium zinc oxide (IZO) are used. A thin film containing a conductive metal oxide such as zinc oxide (ZnO) can be used.

  As the electrolyte layer 3, for example, an iodine-based electrolyte is used. Specifically, an electrolyte component such as iodine, iodide ion or tertiary butyl pyridine dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile is used. The electrolyte layer 3 is not limited to the electrolytic solution, and may be a solid electrolyte.

As the solid electrolyte, for example, is illustrated DMPImI (dimethylpropyl imidazolium iodide) is, in addition, LiI, NaI, KI, CsI, metal iodide such as CaI _2, tetraalkylammonium iodide and quaternary ammonium compounds Bromide such as a combination of iodide such as iodine salt and I ₂ , metal bromide such as LiBr, NaBr, KBr, CsBr and CaBr ₂ , and bromide salt of quaternary ammonium compound such as tetraalkylammonium bromide and Br ₂ And the like can be used as appropriate.

  The photocatalyst film 4 is formed of an oxide semiconductor layer 41 to which a photosensitizing dye 42 is adsorbed, and in the production thereof, the photocatalyst fine particles, that is, the oxide semiconductor that is metal oxide fine particles, together with a viscosity agent is added to an alcohol liquid. The melted paste is applied on the surface of the transparent electrode 1, more precisely on the surface of the buffer layer 5, dried, and then adsorbed with a photosensitizing dye on the oxide semiconductor.

Examples of the oxide semiconductor include metal oxides such as titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), and niobium oxide (Nb ₂ O ₅ ). As photosensitizing dyes, ruthenium complexes and iron complexes having a ligand containing a bipyridine structure or a terpyridine structure, metal complexes of porphyrins or phthalocyanines, or organic dyes such as eosin, rhodamine, merocyanine, coumarin, etc. Is used. Moreover, propanol, t-butyl alcohol, ethoxyethanol, ethanol, etc. are used as an alcohol liquid which is a solvent. Furthermore, for the purpose of suppressing hydrolysis, diethanolamine, acetylacetone, or the like, or if necessary, an acid such as nitric acid, acetic acid, hydrochloric acid may be added. Examples of the viscosity agent include ethylene glycol and acetylacetone.

  Further, the counter electrode 2 has been described on the assumption that the transparent conductive film 22 is formed on the surface of the transparent substrate 21, but a metal sheet such as aluminum, copper, or tin can also be used. In addition, the counter electrode may be configured by holding a gel-like solid electrolyte on a mesh electrode made of metal such as aluminum, copper, tin, or carbon, or conductively bonded to one surface of the transparent substrate 21. The counter electrode 2 is formed by covering the transparent substrate 21 with an agent layer and transferring a separately formed brush-like carbon nanotube group to the transparent substrate 21 side through the adhesive layer. Also good.

The buffer layer 5 provided on the surface of the transparent electrode 1 has a liquid obtained by dissolving a photocatalyst precursor in an alcohol liquid on the surface of the transparent electrode, which is about several nm to several tens nm (preferably several nm to 20 nm). It is formed by spraying with superheated steam and baking after coating with or after coating.

I.e. for example, the surface of the PEN-ITO film as the transparent electrode 1, using a spray method, a metal alkoxide is a photocatalyst precursor (for example, a titanium alkoxide is used) by spraying a liquid to become dissolved in the alcohol solution After coating from the liquid spray nozzle, immediately after that, the superheated steam adjusted to a temperature range exceeding 100 ° C. to 300 ° C. is sprayed from the steam spray nozzle and fired (also referred to as sintering) to obtain a predetermined thickness. For example, the buffer layer 5 of about 10 nm is formed.

In addition, although the film was used for the transparent substrate, you may use a glass substrate. The method for applying the liquid is not limited to the spray method, and an electrostatic spray method, a spin coat method, a dip method, or the like can be used. However, when the substrate surface is rough, the spray method is optimal. Further, the electrostatic spraying is configured to place the needle electrodes on the center of the liquid spray nozzle for applying i.e. spraying liquid towards the transparent electrode, the application electrode for mounting the needle electrode and the transparent electrode A DC power supply with a predetermined voltage is connected between them, and during spraying, a positive voltage is applied to the needle electrode side, so that the spray solution is charged and sprayed onto the surface of the transparent electrode disposed on the negative application electrode. It is the method of making it adhere.

  In addition to titanium alkoxide, titanium tetraethoxide, titanium tetrachloride, titanium hydroxide, or the like can be used as the photocatalyst precursor. The photocatalyst precursor does not necessarily match the material of the photocatalyst film. For example, when the photocatalyst is titanium oxide, a niobium oxide precursor can be used as the precursor.

  Hereinafter, examples specifically showing the method of forming the buffer layer will be described.

In Example 1, 0.05 g of titanium (IV) isopropoxide (TTIP) as a photocatalyst precursor was dissolved in 99.95 g of a propanol solution on the surface of a PEN-ITO film as a transparent electrode using a spray method. Immediately after applying the liquid , the superheated steam adjusted to a temperature range of over 100 ° C. to 300 ° C. was sprayed and fired to form a buffer layer of about 10 nm, for example.

In this case, as shown in FIG. 2, above the transparent electrodes 1, the steam spray nozzle 62 for spraying a liquid spray nozzle 61 and superheated steam H spraying liquid B are juxtaposed, and the liquid B from the liquid spray nozzles 61 The buffer layer 5 is formed on the surface of the transparent electrode 1 by spraying and moving in the direction of arrow a while spraying the superheated steam H from the steam spray nozzle 62.

In addition, what is necessary is just to move the transparent electrode 1 side to the arrow b direction, when not moving both the nozzles 61 and 62. FIG. The relative moving speed is performed within a range of several mm to 1000 mm / sec.
Here, the vapor spray nozzle 62 will be described with reference to FIG.

  That is, the vapor spray nozzle 62 has an elongated box shape in which the lower surface is opened and the upper side surface is provided with an opening (also referred to as a supply port) for saturated water vapor S, and an electric heater (not shown) is provided inside. ) Is placed. Specifically, the ejection opening of the vapor spray nozzle 62 is elongated in the width direction orthogonal to the front-rear movement direction of the transparent electrode 1.

  Accordingly, when saturated steam S of 100 ° C. is supplied to the steam spray nozzle 62, it is heated to a predetermined temperature by the electric heater, for example, to a temperature of over 100 ° C. to 300 ° C., and overheated from the ejection opening on the lower surface. The water vapor H is supplied to the surface of the buffer layer 5. In this sense, it can be said that the steam spray nozzle 62 is provided with a superheated steam generator. The liquid spray nozzle 61 is configured to have an ejection opening that can spray in the same spray range as the vapor spray nozzle 62.

In addition, the application conditions of the liquid by the spray method, that is, the application solution, include nozzle type, application solution viscosity, atomizing air pressure, pattern width, discharge amount, discharge pressure, nozzle moving speed, overlap width, nozzle and application surface. Although the distance with a certain transparent electrode, etc. are mentioned, since these differ with the discharge machine to be used, what is necessary is just to select and apply | coat suitably a coating condition so that a desired film thickness may be obtained. In addition, you may spray in multiple times, when baking by one superheated steam spraying is inadequate.

In Example 1, for example, the atomizing air pressure was 0.3 MPa, the discharge amount was 15 g / min, the distance between the nozzle and the transparent electrode was 20 cm, and the moving speed of the nozzle was 100 m / min.
When a dye-sensitized solar cell having an effective diameter of φ6 mm is produced using a commercially available low-temperature titanium oxide paste without using a buffer layer, the battery performance is 1 sun, the current density is 8.58 mA / under 1.5 AM. cm ^2, the open circuit voltage is 0.71V, while the fill factor 0.62, the conversion efficiency was 3.78% according to that forming the buffer layer by using superheated steam, the current density is 9. 00 mA / cm ² , open-circuit voltage was 0.72 V, fill factor was 0.65, and conversion efficiency was 4.20%. That is, it can be seen that the photocatalytic film forming method according to the present invention is excellent.

Next, a method for forming a buffer layer according to Example 2 will be described.
In Example 2, the buffer layer having the same thickness as that of Example 1 described above is formed by baking with superheated steam in the temperature range of over 100 ° C. to 300 ° C. simultaneously with the formation of the coating film by the spray method. It is to be formed.

That is, as shown in FIG. 4, above the transparent electrodes 1, in the same manner as in Example 1, together with the steam spray nozzle 62 for spraying a liquid spray nozzle 61 and the superheated steam is sprayed (coated) the liquid is juxtaposed, The spray directions are set so that the spray region of the superheated steam from the steam spray nozzle 62 overlaps the spray region (application region) of the spray nozzle 61. Of course, as in the first embodiment, both the nozzles 61 and 62 are moved in the direction of the arrow a, and a buffer layer is formed on the surface of the transparent electrode 1. Similarly to the first embodiment, when both the nozzles 61 and 62 are not moved, the transparent electrode 1 side may be moved in the arrow b direction. The relative moving speed is performed within a range of several mm to 1000 mm / sec.

Next, a method for forming a buffer layer according to Example 3 will be described.
In the formation method of Example 3, the surface of the coating film formed by the spray method is sprayed with superheated steam in the temperature range exceeding 100 ° C. to 300 ° C., and further exceeding 300 ° C. to 500 ° C. In this method, the coating film is fired instantaneously by spraying superheated water vapor in the temperature range.

That is, as shown in FIG. 5, a liquid spray nozzle 61 that sprays liquid and a first steam spray nozzle 62 that sprays superheated steam are juxtaposed above the transparent electrode 1, and a little apart from the first steam spray nozzle 62. A second steam spray nozzle 63 that sprays superheated water vapor is also disposed at the spot, and the liquid electrode 1 is moved while moving the transparent electrode 1 at a speed of several mm / sec to 1000 mm / sec as indicated by an arrow c. After spraying the liquid B from the spray nozzle 61 and simultaneously spraying the low-temperature superheated steam H from 100 ° C. to 300 ° C. from the first steam spray nozzle 62, the second steam spray nozzle 63 further exceeds 300 ° C. The buffer layer is formed by spraying high-temperature superheated steam H ′ up to 500 ° C. In addition, you may move the spray nozzles 61-63 side to the arrow d direction like Example 1 and Example 2 mentioned above, without moving the transparent electrode 1. FIG.

  In this way, superheated steam at different temperatures is sprayed in two stages, that is, spraying superheated steam adjusted to a temperature range exceeding 100 ° C. to 300 ° C. to promote hydrolysis and crystallization of the coating film. Then, by spraying superheated steam adjusted to a temperature range of more than 300 ° C. and up to 500 ° C., a high quality buffer layer can be instantaneously formed.

  More specifically, spraying and baking low-temperature superheated steam promotes hydrolysis and crystallization of titanium oxide, thereby increasing the amount of titanium oxide in the buffer layer. Further, by spraying and baking high-temperature superheated water vapor, the generated titanium oxide particles and the bond between the particles and the transparent electrode become strong, and excess water, alcohol, dust, etc. can be removed. it can.

  In each of the above-described embodiments, the liquid spray nozzle and the steam spray nozzle have been described as having an ejection opening that is elongated in the width direction, but of course, a nozzle having a normal circular ejection opening is used. In this case, in addition to the back-and-forth movement, it is reciprocated in the width direction.

  According to the method for forming a buffer layer according to each of the above embodiments, the photocatalytic film can be formed without the natural drying or the firing step using a heater or the like. Moreover, by using superheated steam, it can be fired without damaging the film and the transparent conductive film.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 2 Counter electrode 3 Electrolyte layer 4 Photocatalyst film 5 Buffer layer 11 Transparent substrate 12 Transparent conductive film 21 Transparent substrate 22 Transparent conductive film 41 Oxide semiconductor layer 42 Photosensitizing dye 61 Liquid spray nozzle 62 Vapor spray nozzle (1st Steam spray nozzle)
63 Second steam spray nozzle

Claims (5)

The transparent electrode and photocatalyst film in a dye-sensitized solar cell comprising a transparent electrode, a counter electrode, an electrolyte layer disposed between the two electrodes, and a photocatalyst film disposed between the electrodes and on the transparent electrode side A method of forming a buffer layer disposed between
A dye formed by applying a liquid obtained by dissolving a precursor of a photocatalyst in an alcohol liquid to the surface of the transparent electrode, or forming a buffer layer by spraying superheated water vapor after baking. A method for forming a buffer layer in a sensitized solar cell.   2. The formation of a buffer layer in a dye-sensitized solar cell according to claim 1, wherein the photocatalyst is titanium oxide, tungsten oxide, tin oxide, zinc oxide or niobium oxide, and the precursor is a metal alkoxide thereof. Method. The method for forming a buffer layer in a dye-sensitized solar cell according to claim 1 or 2, wherein a spray method, a spin coating method, or a dip method is used when applying the liquid to the surface of the transparent electrode.   The method for forming a buffer layer in a dye-sensitized solar cell according to any one of claims 1 to 3, wherein the temperature of the superheated steam is in the range of more than 100 ° C to 300 ° C. The superheated steam is sprayed in two stages, the temperature of the superheated steam sprayed in the first stage is in the range of over 100 ° C. to 300 ° C., and the temperature range of the superheated steam sprayed in the second stage is 300 ° C. The method for forming a buffer layer in a dye-sensitized solar cell according to any one of claims 1 to 3 , wherein the temperature is in the range of up to 500 ° C.

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