JP6221787B2 - Method for producing conductive laminate, method for producing counter electrode for dye-sensitized solar cell, method for producing dye-sensitized solar cell, and method for producing solar cell module - Google Patents

Description

  The present invention relates to a method for producing a conductive laminate, a conductive laminate obtained by using the production method, a counter electrode for a dye-sensitized solar cell using the conductive laminate, and a dye-sensitized solar. The present invention relates to a battery and a solar battery module.

  In recent years, various conductive films using materials other than ITO (indium tin oxide) have been developed as conductive films used for electrodes of solar cells. Specifically, it has been proposed to use a carbon conductive film in which carbon such as carbon nanotubes (hereinafter sometimes referred to as “CNT”) is blended as a conductive material for an electrode of a solar cell (for example, a patent). Reference 1).

  In recent years, organic solar cells such as dye-sensitized solar cells have attracted attention as solar cells to which such a conductive film is applied. Among them, the dye-sensitized solar cell can be expected to be lightweight, can be stably generated in a wide illuminance range, and can be manufactured using a relatively inexpensive material without requiring a large facility. , Attracting particular attention.

Here, as shown in FIG. 1, the dye-sensitized solar cell usually has a photoelectrode 10, a counter electrode (catalyst electrode) 30, and an electrolyte layer 20 positioned between the photoelectrode 10 and the counter electrode 30. (For example, refer to Patent Document 2). The photoelectrode 10 includes a support 10a, a conductive layer 10b provided on the support 10a, a porous semiconductor fine particle layer 10c and a sensitizing dye layer 10d provided on the conductive layer 10b. . The counter electrode 30 includes a support 30a, a conductive layer 30b provided on the support 30a, and a catalyst layer 30c provided on the conductive layer 30b. Furthermore, the conductive layer 10 b of the photoelectrode 10 and the conductive layer 30 b of the counter electrode 30 are connected via an external circuit 40.
In this dye-sensitized solar cell, when the sensitizing dye in the photoelectrode receives light and is excited, the electrons of the sensitizing dye are taken out, and the extracted electrons exit from the photoelectrode and are externally supplied. It moves to the counter electrode through this circuit and further moves to the electrolyte layer.

Japanese Patent No. 5082016 JP 2013-16435 A

  Incidentally, carbon can also function as a catalyst for activating the redox reaction in the counter electrode of the dye-sensitized solar cell. Therefore, when applying a carbon conductive film to the counter electrode of a dye-sensitized solar cell, it is possible to form both a conductive layer and a catalyst layer with a carbon conductive film.

  However, when both the conductive layer of the counter electrode and the catalyst layer are formed of a carbon conductive film, when the carbon conductive film is stacked and used as a conductive laminate, the conductive laminate includes a conductive layer. In addition to the properties, it is required to exhibit desired activities such as catalytic activity.

Therefore, the present invention provides an efficient method for producing a conductive laminate excellent in conductivity and desired activity such as catalytic activity, and conductive laminate excellent in conductivity and desired activity such as catalytic activity. The purpose is to provide a body.
Another object of the present invention is to provide a counter electrode for a dye-sensitized solar cell that is excellent in conductivity and catalytic activity.
Furthermore, an object of this invention is to provide the dye-sensitized solar cell and solar cell module which are excellent in photoelectric conversion efficiency.

  An object of the present invention is to advantageously solve the above-mentioned problems, and the method for producing a conductive laminate of the present invention is based on a carbon dispersion 1 containing carbon 1, a dispersant 1 and a solvent 1. A first carbon layer obtained by applying a carbon dispersion liquid 2 containing carbon 2, a dispersant 2 and a solvent 2 in step (1) to form a first carbon layer by applying on a material and drying; A step (2) of applying and drying to form a second carbon layer; at least the second carbon layer obtained in step (2) is washed with a solvent 3 and at least a part of the dispersant 2; Is selected from the group consisting of plasma treatment, UV treatment and ozone treatment for at least the second carbon layer obtained in step (2). At least one process Go and at least the second carbon layer decomposition step of decomposing a part of the dispersing agent 2 contained in the (4); including. The conductive laminate obtained in this way is excellent in both conductivity and desired activity such as catalytic activity.

  Here, in the method for producing a conductive laminate of the present invention, it is preferable that at least one of the carbon 1 and the carbon 2 includes a carbon nanotube. This is because the inclusion of carbon nanotubes further improves the conductivity and desired activity such as catalytic activity in the resulting conductive laminate. Moreover, it is because the bending resistance of this electroconductive laminated body also improves.

Furthermore, in the method for producing a conductive laminate of the present invention, the carbon nanotube has a BET specific surface area of 600 m ² / g or more and 2600 m ² / g or less by nitrogen adsorption, and a BET specific surface area of 0.1 m or less by water vapor adsorption. 01m is preferably ² / g or more ^{30 m} 2 / g or less. If carbon nanotubes having a BET specific surface area within the above range are used, the conductivity, desired activity such as catalytic activity, and bending resistance can be further improved in the resulting conductive laminate. is there.
In the present invention, the “BET specific surface area” can be determined by measuring the nitrogen adsorption isotherm at 77K and the water vapor adsorption isotherm at 298K, respectively, by the BET method. Here, for the measurement of the BET specific surface area, for example, “BELSORP (registered trademark) -max” (manufactured by Nippon Bell Co., Ltd.) can be used.

Moreover, in the manufacturing method of the electroconductive laminated body of this invention, it is preferable that the average length of the said carbon nanotube is 0.1 micrometer or more and 10 mm or less. If carbon nanotubes having an average length within the above range are used, the resulting conductive laminate can further improve conductivity, desired activity such as catalytic activity, and bending resistance, This is because the carbon layer containing the carbon nanotubes can have a favorable film shape.
In the present invention, the “average length of carbon nanotubes” can be obtained by measuring the length of 100 carbon nanotubes selected at random using a transmission electron microscope.

The conductive laminate of the present invention obtained by the method for producing a conductive laminate of the present invention preferably has a surface resistivity of 0.01Ω / □ or more and 500Ω / □ or less. If the surface resistivity is 0.01Ω / □ or more and 500Ω / □ or less, conductivity and desired activity such as catalytic activity can be achieved at a high level.
In the present invention, “surface resistivity” can be measured by a four-terminal four-probe method using a resistivity meter in accordance with JIS K7194.

  Moreover, this invention aims to solve the said subject advantageously, The counter electrode for dye-sensitized solar cells of this invention is characterized by using the electroconductive laminated body mentioned above. To do. Since this counter electrode for dye-sensitized solar cell uses the conductive laminate described above, it is excellent in conductivity and catalytic activity.

  Furthermore, this invention aims at solving the said subject advantageously, The dye-sensitized solar cell of this invention is equipped with the counter electrode for dye-sensitized solar cells mentioned above. Features. Since this dye-sensitized solar cell uses the counter electrode for the dye-sensitized solar cell described above, it is excellent in photoelectric conversion efficiency.

  And this invention aims to solve the said subject advantageously, The solar cell module of this invention connects the dye-sensitized solar cell mentioned above in series and / or in parallel. It is characterized by. Since this solar cell module uses the dye-sensitized solar cell described above, it is excellent in photoelectric conversion efficiency.

According to the present invention, an efficient method for producing a conductive laminate excellent in conductivity and desired activity such as catalytic activity, and conductive lamination excellent in conductivity and desired activity such as catalytic activity. The body can be provided.
Moreover, according to this invention, the counter electrode for dye-sensitized solar cells which is excellent in electroconductivity and catalytic activity can be provided.
Furthermore, according to this invention, the dye-sensitized solar cell and solar cell module which are excellent in photoelectric conversion efficiency can be provided.

It is a figure which shows schematic structure of a dye-sensitized solar cell.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the method for producing a conductive laminate of the present invention can be used when producing a carbon-containing conductive laminate excellent in conductivity and desired activity such as catalytic activity. And the conductive laminated body manufactured using the manufacturing method of the conductive laminated body of this invention is not specifically limited, The counter electrode for dye-sensitized solar cells, a dye-sensitized solar cell, and a solar cell module It can be used for various products.

(Method for producing conductive laminate)
The method for producing a conductive laminate according to the present invention includes a step (1) of forming a first carbon layer by applying a carbon dispersion 1 containing carbon 1, a dispersant 1 and a solvent 1 on a substrate and drying it. A step (2) of applying a carbon dispersion 2 containing carbon 2, a dispersant 2 and a solvent 2 on the first carbon layer obtained in step (1) and drying to form a second carbon layer; At least the second carbon layer obtained in the step (2) is washed with the solvent 3, and at least a part of the dispersant 2 is removed from the second carbon layer (3), and / or at least The second carbon layer obtained in the step (2) is subjected to at least one treatment selected from the group consisting of plasma treatment, UV treatment and ozone treatment, and at least contained in the second carbon layer. Dispersant 2 Some decomposing decomposition step (4) and; including.
And in the conductive laminate of the present invention obtained by using the method for producing a conductive laminate of the present invention, the first carbon layer and the second carbon layer include the dispersant 1 and the dispersant 2, respectively. The dispersant 2 is mainly removed from the second carbon layer by the washing step (3) and / or the decomposition step (4), and the carbon 2 content in the second carbon layer is the carbon 1 content in the first carbon layer. Is bigger than. Such a conductive laminate is excellent in both conductivity and desired activity such as catalytic activity.

<Step (1)>
In the step (1), a carbon dispersion 1 containing carbon 1, a dispersant 1 and a solvent 1 is applied onto a substrate, and the applied carbon dispersion 1 is dried to form a conductive laminate. A carbon layer is formed. The carbon dispersion 1 may optionally further contain other additives.

[Carbon 1]
The carbon 1 of the first carbon layer is not particularly limited, and conductive carbon such as natural graphite, activated carbon, artificial graphite, ketjen black, acetylene black, carbon nanofiber, and carbon nanotube (CNT) is used. it can. Among them, as the carbon 1, it is preferable to use CNT. This is because CNT is excellent in conductivity and mechanical properties, and if CNT is used for the first carbon layer, the conductivity and bending resistance of the first carbon layer can be improved.
In addition, the conductive carbon mentioned above may be used individually by 1 type, and may mix and use 2 or more types.

[[carbon nanotube]]
Here, carbon nanotubes suitable as carbon 1 are not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. It is preferable that there is a single-walled carbon nanotube. If single-walled carbon nanotubes are used, the conductivity and mechanical properties of the carbon layer can be improved compared to the case where multi-walled carbon nanotubes are used.

Here, as the CNT, a CNT having a ratio (3σ / Av) of a value (3σ) obtained by multiplying the standard deviation (σ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20 and less than 0.60 is used. It is preferable to use CNTs with 3σ / Av exceeding 0.25, and it is even more preferable to use CNTs with 3σ / Av exceeding 0.50. If CNTs having 3σ / Av of more than 0.20 and less than 0.60 are used, the dispersibility of the CNTs is increased, and the conductivity and mechanical properties of the carbon layer are sufficiently enhanced even when the amount of CNTs is small. be able to. Therefore, it is possible to obtain a carbon layer having excellent conductivity, mechanical properties, and transparency by reducing the amount of CNTs necessary for obtaining a carbon layer having desired conductivity and mechanical properties.
“Average diameter of carbon nanotube (Av)” and “standard deviation of diameter of carbon nanotube (σ: sample standard deviation)” are respectively 100 carbon nanotubes randomly selected using a transmission electron microscope. It can be determined by measuring the diameter (outer diameter). The average diameter (Av) and standard deviation (σ) of CNTs may be adjusted by changing the CNT manufacturing method and manufacturing conditions, or by combining multiple types of CNTs obtained by different manufacturing methods. May be.

  In the present invention, as the CNT, the diameter measured as described above is plotted on the horizontal axis and the frequency is plotted on the vertical axis. The

  Furthermore, the CNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.

  In addition, the ratio of the G band peak intensity to the D band peak intensity in the Raman spectrum (G / D ratio) of CNT is usually 1 or more and 100 or less, preferably 50 or less, more preferably 20 or less. When the G / D ratio is 1 or more and 100 or less, the conductivity and mechanical properties of the carbon layer can be sufficiently improved even if the amount of CNT is small. Therefore, it is possible to obtain a carbon layer having excellent conductivity, mechanical properties, and transparency by reducing the amount of CNTs necessary for obtaining a carbon layer having desired conductivity and mechanical properties.

  Furthermore, the average diameter (Av) of CNTs is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, and more preferably 10 nm or less. If the average diameter (Av) of CNT is 0.5 nm or more, it is possible to obtain a carbon layer excellent in conductivity and mechanical properties by suppressing the aggregation of CNT and improving the dispersibility of CNT in the carbon layer. . Moreover, if the average diameter (Av) of CNT is 15 nm or less, the carbon layer which is excellent in electroconductivity and mechanical characteristics can be obtained.

  The average length of the CNT is preferably 0.1 μm or more, more preferably 1.0 μm or more, and preferably 10 mm or less. If the average length of CNTs is 0.1 μm or more, even if the amount of CNTs is small, the conductivity and mechanical properties of the carbon layer can be sufficiently enhanced, and the CNTs are intertwined and are good Since the network structure is formed, the shape of the carbon layer can be made a good film shape. Further, if the average length of CNTs is 10 mm or less, excessive aggregation of CNTs can be suppressed to increase the dispersibility of CNTs in the carbon layer, and a carbon layer having excellent conductivity and mechanical properties can be obtained. .

Further, the BET specific surface area by nitrogen adsorption of CNTs is preferably 600 m ² / g or more, and preferably 2600 m ² / g or less. Further, the BET specific surface area by water vapor adsorption of CNTs is preferably 0.01 m ² / g or more, and preferably 30 m ² / g or less.
Here, the BET specific surface area by nitrogen adsorption corresponds to the specific surface area for the entire surface of CNT, whereas the BET specific surface area by water vapor adsorption corresponds to the specific surface area for the hydrophilic surface portion of CNT. To do. Therefore, when the BET specific surface area by nitrogen adsorption and the BET specific surface area by water vapor adsorption are within the above ranges, a hydrophilic surface portion is appropriately present on the surface of the CNT, and the dispersibility of the CNT is excellent. Moreover, if the BET specific surface area by nitrogen adsorption is 600 m < ² > / g or more, the electroconductivity and mechanical characteristic of a carbon layer can fully be improved. Furthermore, if the BET specific surface area by nitrogen adsorption is 2600 m ² / g or less, agglomeration of CNTs is suppressed and the dispersibility of CNTs in the carbon layer is enhanced, and a carbon layer having excellent conductivity and mechanical properties is obtained. Can do.

Furthermore, it is preferable that the mass density of CNT is 0.002 g / cm ³ or more and 0.2 g / cm ³ or less. If the mass density is 0.2 g / cm ³ or less, the CNTs become weakly bonded, so that the CNTs can be uniformly dispersed to obtain a carbon layer having excellent conductivity and mechanical properties. In addition, if the mass density is 0.002 g / cm ³ or more, the integrity of the CNTs can be improved and the variation can be suppressed, so that handling becomes easy.

Further, the CNT preferably has a plurality of micropores. Among them, the CNT preferably has micropores having a pore size smaller than 2 nm, and the abundance thereof is preferably a micropore volume, preferably 0.40 mL / g or more, more preferably 0.43 mL / g or more, Preferably, it is 0.45 mL / g or more, and the upper limit is usually about 0.65 mL / g. Since the CNTs have the above micropores, the aggregation of the CNTs is suppressed, the dispersibility of the CNTs in the carbon layer is increased, and a carbon layer having excellent conductivity and mechanical properties can be efficiently obtained. . The micropore volume can be adjusted, for example, by appropriately changing the CNT preparation method and preparation conditions.
Here, the “micropore volume (Vp)” is an equation in which the nitrogen adsorption / desorption isotherm at the liquid nitrogen temperature (77 K) of CNT is measured and the nitrogen adsorption amount at relative pressure P / P0 = 0.19 is V. (I): Vp = (V / 22414) × (M / ρ). Here, P is a measurement pressure at the time of adsorption equilibrium, P0 is a saturated vapor pressure of liquid nitrogen at the time of measurement, and in formula (I), M is an adsorbate (nitrogen) molecular weight of 28.010, and ρ is an adsorbate (nitrogen). ) At 77K with a density of 0.808 g / cm ³ . The micropore volume can be easily determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).

  The CNT having the above-described properties is obtained by supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for CNT production on the surface (hereinafter, also referred to as “CNT production base material”), for example. When synthesizing CNTs by chemical vapor deposition (CVD), the catalytic activity of the catalyst layer for CNT production is dramatically increased by the presence of a small amount of oxidizing agent (catalyst activation material) in the system. In a method of improving (super growth method; see International Publication No. 2006/011655), a catalyst layer is formed on the surface of a substrate by a wet process, and a source gas containing acetylene as a main component (for example, 50 volumes of acetylene) %), It can be produced efficiently. Hereinafter, the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.

[Dispersant 1]
The dispersant 1 is not particularly limited as long as it can disperse the carbon 1, and examples thereof include surfactants, synthetic polymers, and natural polymers.

Here, as the surfactant, any anionic surfactant, cationic surfactant, or nonionic surfactant can be used. Specific examples of the surfactant include sodium dodecyl sulfonate, sodium deoxycholate, sodium cholate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl oxide disulfonate, and the like.
Synthetic polymers include, for example, polyethylene, polypropylene, polystyrene, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, polystyrene sulfonic acid, synthetic polymers containing sulfonic acid group-containing monomer units and carboxy group-containing monomer units. Molecule, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer resin, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy resin Phenoxy ether resin, phenoxy ester resin, fluorine resin, melamine resin, alkyd resin, phenol resin, polyacrylamide, polyacrylic acid and the like.
Examples of natural polymers include polysaccharides such as starch, pullulan, dextran, dextrin, guar gum, xanthan gum, amylose, amylopectin, alginic acid, gum arabic, carrageenan, chondroitin sulfate, hyaluronic acid, curdlan, chitin, chitosan, cellulose, And salts or derivatives thereof. The derivative means a conventionally known compound such as ester or ether.

Among the above, the dispersant 1 is preferably a synthetic polymer or a natural polymer because it can function as a binder for binding carbons or a carbon layer to a substrate on which the carbon layer is formed. is there. Among them, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, polystyrene sulfonic acid, and a synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit are more preferable. A synthetic polymer containing a monomer unit and a carboxy group-containing monomer unit is particularly suitable.
In addition, the dispersing agent 1 can be used individually or in combination of 2 or more types, respectively.

  Hereinafter, a synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit will be described. In the present invention, “comprising a monomer unit” means “a monomer-derived structural unit is contained in a polymer obtained using the monomer”.

Here, the sulfonic acid group-containing monomer capable of forming a sulfonic acid group-containing monomer unit includes a sulfonic acid group and a group copolymerizable with another monomer such as a carbon-carbon unsaturated bond. Although it will not specifically limit if it has, For example, aromatic sulfonic acids, such as styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, acrylamide-t-butyl-sulfonic acid, acrylamide-N-butanesulfonic acid etc. are mentioned. Can do. Here, in the sulfonic acid group-containing monomer, a hydrogen atom in the sulfonic acid group may be substituted with an inorganic ion or an organic ion to form an inorganic salt or an organic salt. That is, the sulfonic acid group-containing monomer may be in the form of a sulfonate.
Examples of inorganic salts include alkali metal salts (lithium, sodium, potassium, etc.), and examples of organic salts include alkylamine salts (methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, trimethylamine). Propylamine, tributylamine, tri-t-butylamine and the like) and arylamine (phenylamine, benzylamine and the like).

  Among these, sulfonic acid group-containing monomers include aromatic sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid, acrylamide-t-butyl-sulfonic acid, and alkali metal salts (sodium, potassium) thereof. Preferably, alkali metal salts (sodium and potassium) of styrene sulfonic acid are more preferable.

  In the synthetic polymer containing the sulfonic acid group-containing monomer unit and the carboxy group-containing monomer unit, the ratio of the sulfonic acid group-containing monomer unit to the total monomer units is usually 10 mol%. Or more, preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more, and usually 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, particularly Preferably it is 60 mol% or less.

The carboxy group-containing monomer capable of forming a carboxy group-containing monomer unit is one having a carboxy group and a group copolymerizable with another monomer such as a carbon-carbon unsaturated bond. Examples thereof include, but are not limited to, ethylenically unsaturated aliphatic carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid, 4-vinylbenzoic acid, and the like. Here, in the carboxy group-containing monomer, a hydrogen atom in the carboxy group may be substituted with an inorganic ion or an organic ion to form an inorganic salt or an organic salt. That is, the carboxy group-containing monomer may be in the form of a carboxylate.
Here, as an inorganic salt and an organic salt, the thing similar to the sulfonic acid group containing monomer mentioned above is mentioned.

  Among these, ethylenically unsaturated aliphatic carboxylic acids and salts thereof are preferable, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and salts thereof are more preferable, and maleic acid and alkali metal salts thereof (sodium) Salt, potassium salt) is particularly preferred.

  In the synthetic polymer containing the sulfonic acid group-containing monomer unit and the carboxy group-containing monomer unit, the ratio of the carboxy group-containing monomer unit to the total monomer units is usually 10 mol% or more. , Preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 40 mol% or more, usually 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, particularly preferably Is 60 mol% or less.

  In addition, the synthetic polymer including the sulfonic acid group-containing monomer unit and the carboxy group-containing monomer unit may be arbitrarily repeated in addition to the above-described sulfonic acid group-containing monomer unit and carboxy group-containing monomer unit. Units may be included. Other monomers that can form such optional repeating units include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate, etc.), methacrylic acid esters (methacrylic acid). Methyl acetate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, etc.), itaconic acid ester (such as methyl itaconate, ethyl itaconate, propyl itaconate, butyl itaconate, benzyl itaconate), styrene, acrylonitrile Methacrylonitrile, acrylic acid amide, methacrylic acid amide, itaconic acid amide, N, N-dimethylacrylamide and the like.

  In the synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit, the content of any repeating unit is preferably 30 mol% or less, more preferably 20 mol% or less, Still more preferably, it is 10 mol%, Especially preferably, it is 5 mol% or less.

A synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit is produced, for example, by polymerizing a monomer composition containing the above-described monomer in a reaction solvent. Is done.
Here, the content ratio of each monomer in the monomer composition is usually the same as the content ratio of the corresponding monomer unit (repeating unit) in the desired synthetic polymer.
Known solvents, polymerization methods, polymerization initiators, and the like can be appropriately selected and used.

  The number average molecular weight of the synthetic polymer including the sulfonic acid group-containing monomer unit and the carboxy group-containing monomer unit is not particularly limited, but is preferably 1 million to 25 million, more preferably 200. It is 10 to 15 million, more preferably 3 to 10 million. Here, the number average molecular weight is calculated by using a gel permeation chromatography method using water as an eluent and comparing it with a calibration curve using standard polyethylene glycol.

Specific examples of the synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit are described below, but the sulfonic acid group-containing monomer unit and the carboxy group-containing monomer unit are described below. However, the synthetic polymer containing is not limited to these. In the following examples, “molar ratio” indicates the molar ratio of each monomer unit in the synthetic polymer.
-Copolymer of sodium styrene sulfonate / sodium acrylate (molar ratio = 1/1, average degree of polymerization 20,000, number average molecular weight 3 million 2300)
-Copolymer of sodium styrenesulfonate / sodium methacrylate (molar ratio = 1/1, average polymerization degree 30,000, number average molecular weight 47288500)
-Copolymer of sodium styrene sulfonate / potassium methacrylate (molar ratio = 2/1, average degree of polymerization 50,000, number average molecular weight 871,0400)
-Copolymer of sodium styrenesulfonate / disodium itaconate (molar ratio = 3/1, average polymerization degree 50,000, number average molecular weight 9,907,800)
-Copolymer of sodium styrenesulfonate / disodium maleate (molar ratio = 1/1, average degree of polymerization 20,000, number average molecular weight 366.2300)
-Copolymer of sodium styrenesulfonate / disodium maleate (molar ratio = 1/1, average degree of polymerization 50,000, number average molecular weight 91,55,700)
-Copolymer of sodium styrenesulfonate / disodium maleate (molar ratio = 1/1, average degree of polymerization 90,000, number average molecular weight 1,648,800,300)
-Copolymer of sodium styrenesulfonate / disodium maleate (molar ratio = 3/1, average degree of polymerization 20,000, number average molecular weight 3893,000)
-Copolymer of ammonium styrenesulfonate / diammonium maleate (molar ratio = 1/1, average degree of polymerization 30,000, number average molecular weight 5,266,700)
Copolymer of styrene sulfonic acid / maleic acid (molar ratio = 1/1, average degree of polymerization 20,000, number average molecular weight 322,000)
-Copolymer of sodium styrenesulfonate / disodium fumarate (molar ratio = 1/1, average degree of polymerization 20,000, number average molecular weight 36663300)
-Copolymer of sodium vinyl sulfonate / sodium acrylate (molar ratio = 1/1, average degree of polymerization 50,000, number average molecular weight 22.241400)
・ Copolymer of sodium allyl sulfonate / sodium acrylate (molar ratio = 1/1, average degree of polymerization 20,000, number average molecular weight 23,811,600)
Copolymer of acrylamide-sodium N-butanesulfonate / sodium acrylate (molar ratio = 1/1, average degree of polymerization 80,000, number average molecular weight 12051,600)
-Copolymer of sodium styrenesulfonate / disodium maleate / acrylic acid amide (molar ratio = 2/2/1, average polymerization degree 30,000, number average molecular weight 5577300)
Copolymer of sodium styrenesulfonate / disodium maleate / monomethyl sodium maleate (molar ratio = 2/2/1, average degree of polymerization 15,000, number average molecular weight 2977600)
Copolymer of sodium styrenesulfonate / disodium maleate / sodium acrylate (molar ratio = 3/2/1, average polymerization degree 25,000, number average molecular weight 4977300)

  By using a synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit, carbon can be dispersed well, and the substrate and the first carbon layer can be favorably dispersed. Can be glued. Furthermore, normally, the dispersant often becomes a resistance in the carbon layer, and can reduce the conductivity of the carbon layer and the conductive laminate. However, a synthetic polymer containing a sulfonic acid group-containing monomer unit and a carboxy group-containing monomer unit disperses carbon very well, so that it has substantially no influence as a resistance factor and has excellent conductivity. Carbon layer and conductive laminate can be obtained.

[Optional additives]
As optional additives to be blended in the first carbon layer, known additives such as fillers, stabilizers, colorants, charge control agents, lubricants, metal nanoparticles are used depending on the use of the conductive film to be produced. Can be used.

[Formation of the first carbon layer]
The first carbon layer is formed by mixing each of the above components with the solvent 1 to obtain the carbon dispersion 1, applying it on a substrate, and drying it.

  Examples of the solvent 1 include, but are not limited to, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, Alcohols such as amyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, dioxane and tetrahydrofuran, N, N-dimethylformamide, N -Amide polar organic solvents such as methylpyrrolidone, and aromatic hydrocarbons such as toluene, xylene, chlorobenzene, orthodichlorobenzene, and paradichlorobenzene. These may be used alone or in combination of two or more.

  The carbon dispersion 1 is a known mixing and dispersing machine (for example, a ball mill, a bead mill, a sand mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer). And an ultrasonic device, an attritor, a dissolver, a paint shaker, etc.).

  The substrate on which the carbon dispersion liquid 1 is applied is not particularly limited, and a known substrate can be used depending on the use of the conductive laminate to be produced. For example, a resin base material, a glass base material, etc. can be mentioned. Resin base materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and alicyclic. The base material which consists of an acrylic resin, a cycloolefin resin, a triacetyl cellulose etc. can be mentioned. Examples of the glass substrate include a substrate made of ordinary soda glass.

  And as a method of apply | coating the carbon dispersion liquid 1 on a base material, a well-known coating method is employable. Specifically, the coating method includes dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, gravure offset method, etc. Can be used.

  Furthermore, as a method for drying the applied carbon dispersion 1, a known drying method can be employed. Examples of the drying method include a hot air drying method, a vacuum drying method, a hot roll drying method, and an infrared irradiation method. The drying temperature is not particularly limited, but is usually room temperature to 200 ° C., and the drying time is not particularly limited, but is usually 0.1 to 150 minutes.

<Step (2)>
In the step (2), a carbon dispersion 2 containing carbon 2, a dispersant 2 and a solvent 2 is applied on the first carbon layer obtained in the step (1), and the applied carbon dispersion 2 is dried. Then, the second carbon layer constituting the conductive laminate is formed. The second carbon layer may be formed directly on the first carbon layer, or may be formed on the first carbon layer via any additional layer within the range where the effects of the present invention are exhibited. The carbon dispersion 2 may optionally further contain other additives.

[Carbon 2]
The carbon 2 of the second carbon layer is not particularly limited, and conductive carbon similar to the carbon 1 of the first carbon layer can be used. Among them, as the carbon 2, it is preferable to use ketjen black, acetylene black, carbon nanofiber, and CNT. In particular, CNT has excellent catalytic activity in addition to conductivity and mechanical properties, and if CNT is used, conductivity, desired activity such as catalytic activity, and flex resistance can be improved. Therefore, it is preferable.

  In addition, it is preferable that CNT used as carbon 2 has the same property as the suitable property of CNT that can be used as carbon 1 of the first carbon layer. Since the CNTs having the properties described above are excellent in catalytic activity in addition to conductivity and mechanical properties, if the CNTs described above are used, conductivity, desired activity such as catalytic activity, and flex resistance are obtained. And can be further improved.

[Dispersant 2]
The dispersant 2 is not particularly limited as long as the carbon 2 can be dispersed, and examples thereof include the same as those described above with respect to the first carbon layer. As will be described later, in the production of the conductive laminate of the present invention, since the dispersant 2 is removed from the second carbon layer by washing and / or decomposition, examples of the dispersant 2 include sodium dodecylbenzenesulfonate and dodecyldiphenyl. Those that can be easily removed by washing and / or decomposition, such as sodium oxide disulfonate, carboxymethylcellulose, and hydroxyethylcellulose, are preferred.

[Optional additives]
As an arbitrary additive compounded in the second carbon layer, the same additive as that of the first carbon layer can be used.

[Formation of second carbon layer]
The second carbon layer is formed by mixing each of the above components with the solvent 2 to obtain the carbon dispersion 2, applying it on the first carbon layer obtained in the step (1), and drying it.
Here, examples of the solvent 2 include the same as the solvent 1.
In addition, formation of a 2nd carbon layer can be performed by apply | coating this on the said 1st carbon layer, and drying after obtaining the carbon dispersion liquid 2 according to the case of a 1st carbon layer.

  And in the manufacturing method of the electroconductive laminated body of this invention, after a process (2), at least one of the following processes (3) and processes (4) is performed. In addition, it is preferable to perform both the step (3) and the step (4) from the viewpoint of more efficiently removing the dispersant 2 from the second carbon layer.

<Step (3)>
In the step (3), at least the second carbon layer obtained in the step (2) is washed with the solvent 3, and at least a part of the dispersant 2 is removed from the second carbon layer. In this step, the first carbon layer may be washed at the same time, and a part of the dispersant 1 contained in the first carbon layer may be removed.
If the said washing | cleaning is performed with respect to the laminated body which consists of the 1st carbon layer obtained by the process (1) and the process (2) and the 2nd carbon layer formed on the said 1st carbon layer, for example. Good. In the cleaning, the laminate and the solvent 3 capable of dissolving the dispersant 2 are brought into contact with each other, and the dispersant 2 in the second carbon layer is eluted in the solvent 3 to thereby disperse the dispersant 2 in the second carbon layer. Is removed from the second carbon layer. At this time, a part of the dispersant 1 may be removed from the first carbon layer.

  In addition, as the solvent 3 which can melt | dissolve the dispersing agent 2, the same thing as the solvent 2 of the carbon dispersion liquid 2 can be used, without being specifically limited. Among these, from the viewpoint of easy handling, the solvent 3 is preferably water, alcohols, ketones such as acetone and methyl isobutyl ketone, amide polar organic solvents such as N-methylpyrrolidone, and the like.

And washing | cleaning of the laminated body using the solvent 3 mentioned above can be performed by the immersion to the solvent 3 of a laminated body, or the application | coating to the laminated body of the solvent 3, for example. In addition, you may perform a washing | cleaning of a laminated body in multiple times. Moreover, the laminated body after washing | cleaning can be dried using a known method.
In addition, when removing the dispersing agent 2 by immersion in the solvent 3, the immersion time is preferably 30 seconds or longer, more preferably 1 minute or longer, and 30 minutes or longer. More preferred is 1 hour or longer. Moreover, it is preferable to set it as 6 hours or less, and it is more preferable to set it as 3 hours or less. This is because the dispersant 2 can be sufficiently removed if the immersion time is 30 seconds or longer. Further, if the immersion time is 6 hours or less, the dispersant 2 can be sufficiently removed, and the carbon is dropped from the first or second carbon layer by excessive washing, or the laminate is peeled off from the substrate. This is because it can be prevented.

<Process (4)>
In step (4), at least one treatment selected from the group consisting of plasma treatment, UV treatment and ozone treatment (hereinafter referred to as “decomposition treatment”) is performed on at least the second carbon layer obtained in step (2). And at least a part of the dispersant 2 contained in the second carbon layer is decomposed. In this step, the first carbon layer may be simultaneously decomposed, and a part of the dispersant 1 contained in the first carbon layer may be decomposed.
In addition, when performing both a process (3) and a process (4), it is preferable to perform a decomposition process at a process (4) with respect to the 2nd carbon layer which passed through the washing | cleaning at a process (3). That is, when performing both step (3) and step (4), it is preferable to decompose in step (4) the dispersant 2 remaining in the second carbon layer after washing in step (3). .

  What is necessary is just to perform the said decomposition process with respect to the laminated body which consists of a 1st carbon layer and the 2nd carbon layer formed on the said 1st carbon layer, for example. In the decomposition treatment of the laminate, at least one dispersant selected from the group consisting of plasma treatment, UV treatment, and ozone treatment is performed on the laminate, so that at least the dispersant contained in the second carbon layer. Disassemble part of 2. At this time, a part of the dispersant 1 in the first carbon layer may be decomposed. In addition, you may remove the decomposition product produced in the case of a decomposition process using methods, such as washing | cleaning, after performing a decomposition process arbitrarily.

[Plasma treatment]
Here, in the plasma treatment of the laminate, the dispersant 2 present in the second carbon layer is decomposed by exposing the laminate to plasma. Specifically, the plasma treatment of the laminate is performed by placing the laminate in a vessel containing argon, neon, helium, nitrogen, nitrogen dioxide, oxygen, air, etc. This can be done by exposing the two-carbon layer). In addition, (1) DC discharge and low frequency discharge, (2) radio wave discharge, (3) microwave discharge, etc. can be used as a discharge form of plasma generation.
The conditions for the plasma treatment are not particularly limited, but the treatment intensity is preferably such that the energy output per unit area of the plasma irradiation surface is 0.05 to 2.0 W / cm ² , and the gas pressure is 5-150 Pa is preferable. The treatment time may be selected as appropriate, but is usually 1 to 300 minutes, preferably 10 to 180 minutes, more preferably 15 to 60 minutes.

[UV treatment]
In the UV treatment of the laminate, the dispersant 2 present in the second carbon layer is decomposed by irradiating the laminate with ultraviolet rays (UV). Specifically, in the UV treatment of the laminate, ultraviolet rays emitted from an ultraviolet light source such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, a carbon arc lamp, or an ultraviolet laser generator are laminated in the air. Irradiate the body (especially the second carbon layer). In addition, you may process the surface of the 2nd carbon layer of a laminated body with a ultraviolet absorber before irradiation of an ultraviolet-ray.
Here, although the wavelength of the ultraviolet rays with which the laminate is irradiated can be appropriately selected, the wavelength of the ultraviolet rays is preferably 300 nm or more, preferably 500 nm or less, and more preferably 360 nm or less.
In addition, the ultraviolet irradiation is performed by appropriately setting the irradiation time and the intensity of the ultraviolet ray in consideration of the amount of the dispersant 2 present in the second carbon layer and the removal rate of the target dispersant 2. The irradiation time of ultraviolet rays is usually 30 seconds to 6 hours, more preferably 1 minute to 2 hours, and further preferably 1 hour or less.

[Ozone treatment]
In the ozone treatment of the laminate, the dispersant 2 present in the second carbon layer is decomposed by bringing the laminate and ozone molecules into contact with each other. Specifically, the ozone treatment of the laminated body is performed by exposing the laminated body (particularly, the second carbon layer) to ozone. The exposure method can be performed by an appropriate method such as a method of holding the laminate in an atmosphere in which ozone is present for a predetermined time, or a method of bringing an ozone air current into contact with the second carbon layer of the laminate for a predetermined time.
Here, the ozone to be brought into contact with the laminate can be generated by supplying an oxygen-containing gas such as air, oxygen gas, or oxygen-added air to the ozone generator. The obtained ozone-containing gas is introduced into a container, a treatment tank or the like that holds the laminated body, and ozone treatment is performed. Various conditions such as the ozone concentration in the ozone-containing gas, the exposure time, and the exposure temperature are appropriately determined in consideration of the amount of the dispersant 2 present in the second carbon layer and the removal rate of the target dispersant 2. be able to. Specifically, the ozone treatment uses, for example, an oxygen or air stream to generate an ozone-containing gas having a concentration of 1 to 200 mg / L, a flow rate of 20 to 2000 mL / min, and a temperature of 0 to 80 ° C. for 1 minute. Can be performed for ~ 24 hours.

  From the viewpoint of ease of processing, it is preferable to use at least UV processing as the decomposition processing.

  Here, when the above-described cleaning and / or decomposition treatment is performed, the amount of the dispersant 2 in the second carbon layer is decreased, and the content ratio of the carbon 2 in the second carbon layer is improved. When CNTs having a long length, such as SGCNT, are used, the CNTs are entangled with each other to form a network structure. Therefore, even if the dispersant 2 is removed, the layer shape can be maintained well.

In addition, when forming an electroconductive laminated body using the washing | cleaning and / or decomposition | disassembly process mentioned above, the synthetic polymer which contains a sulfonic acid group containing monomer unit and a carboxy group containing monomer unit as the dispersing agent 1 It is preferable to use at least one selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxide disulfonate, carboxymethylcellulose and hydroxyethylcellulose as dispersant 2. If such a dispersant is used in combination, the dispersion contained in the second carbon layer by washing and / or decomposition treatment while adhering the substrate and the laminate satisfactorily with the dispersant 1 contained in the first carbon layer. This is because the agent 2 can be removed satisfactorily.
In addition, a washing | cleaning and a decomposition process may be implemented with respect to the laminated body formed on the base material, and may be implemented with respect to the laminated body peeled from the base material.

(Conductive laminate)
As described above, the conductive laminate of the present invention is obtained. By performing the above-described cleaning and / or decomposition treatment, in particular, the content ratio of the dispersant 2 contained in the second carbon layer is reduced, while the content ratio of the carbon 2 contained in the second carbon layer is increased. As a result, the content ratio of carbon 2 in the second carbon layer is greater than the content ratio of carbon 1 in the first carbon layer on a mass basis. Further, the dispersant 2 present on the surface of the second carbon layer is removed, and more carbon 2 is exposed on the surface of the second carbon layer. Therefore, in the conductive laminate of the present invention, the catalytic activity of the second carbon layer is particularly improved.

<Properties of conductive laminate>
The conductive laminate of the present invention preferably has a surface resistivity of 0.01Ω / □ or more and 500Ω / □ or less. If the surface resistivity is 500Ω / □ or less, sufficiently high conductivity can be obtained. Moreover, if surface resistivity is 0.01 ohm / square or more, it is not necessary to mix | blend carbon abundantly and the fall of transparency can be suppressed. The surface resistivity can be adjusted by changing the amount and type of carbon.

(Dye-sensitized solar cell)
As shown in FIG. 1, the dye-sensitized solar cell 100 according to the present invention includes a photoelectrode 10, an electrolyte layer 20, and a counter electrode 30, and the electrolyte layer 20 is opposed to the photoelectrode 10. It is located between the electrodes 30. The photoelectrode 10 is adsorbed on the surface of the semiconductor fine particles of the support 10a, the conductive layer 10b provided on the support 10a, the porous semiconductor fine particle layer 10c made of semiconductor fine particles, and the porous semiconductor fine particle layer 10c. A sensitizing dye layer 10d made of the sensitizing dye, and the porous semiconductor fine particle layer 10c and the sensitizing dye layer 10d are formed on the conductive layer 10b. The counter electrode 30 includes a support 30a, a conductive layer 30b provided on the support 30a, and a catalyst layer 30c provided on the conductive layer 30b. Furthermore, the conductive layer 10 b of the photoelectrode 10 and the conductive layer 30 b of the counter electrode 30 are connected via an external circuit 40.

  Here, the dye-sensitized solar cell 100 according to the present invention is characterized by using the following counter electrode for a dye-sensitized solar cell according to the present invention as the counter electrode 30. And since the dye-sensitized solar cell 100 is using the counter electrode for dye-sensitized solar cells which is excellent in electroconductivity and catalytic activity, it is excellent in photoelectric conversion efficiency.

<Counter electrode for dye-sensitized solar cell>
The counter electrode 30 according to the present invention can be formed using a conventionally known one except that the conductive laminate described above is used as the conductive layer 30b and the catalyst layer 30c.

  Therefore, a transparent resin substrate or a glass substrate can be used as the support 30a of the counter electrode 30, and it is particularly preferable to use a transparent resin substrate. The transparent resin used for forming the transparent resin substrate includes cycloolefin polymer (COP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC ), Polyarylate (PAr), polysulfone (PSF), polyestersulfone (PES), polyetherimide (PEI), transparent polyimide (PI) and the like.

In the counter electrode 30 according to the present invention, the first carbon layer of the conductive laminate described above is used as the conductive layer 30b, and the second carbon layer of the conductive laminate is used as the catalyst layer 30c. One of them. That is, the counter electrode 30 according to the present invention is prepared by forming a conductive laminate on the support 30a so that the first carbon layer is on the support 30a side.
In the counter electrode 30 using such a conductive laminate, since the second carbon layer exhibits excellent catalytic activity and the conductive laminate exhibits excellent conductivity, the catalytic activity and conductivity are improved. Is excellent.

<Photoelectrode for dye-sensitized solar cell>
As the dye-sensitized solar cell photoelectrode 10, a conventionally known one can be used.

  Specifically, as the support 10 a of the photoelectrode 10, the same support as the support 30 a of the counter electrode 30 can be used.

  The conductive layer 10b is not particularly limited, and is a conductive film made of an oxide such as indium tin oxide (ITO) or indium zinc oxide (IZO), PEDOT [poly (3,4-ethylenedioxythiophene) ] / Conductive carbon such as polythiophene and polyaniline, such as polythiophene and polyaniline, conductive graphite such as natural graphite, activated carbon, artificial graphite, graphene, carbon nanotube (CNT) A conductive film can be used.

  The porous semiconductor fine particle layer 10c of the photoelectrode 10 can be formed using, for example, metal oxide particles (semiconductor fine particles) such as titanium oxide, zinc oxide, and tin oxide. The porous semiconductor fine particle layer 10c can be formed by a press method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, a binder-free coating method, or the like.

Further, as the sensitizing dye that is adsorbed on the surface of the semiconductor fine particles of the porous semiconductor fine particle layer 10c to form the sensitizing dye layer 10d, cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarins. Examples thereof include organic dyes such as dyes, riboflavin dyes, and perylene dyes; metal complex dyes such as phthalocyanine complexes and porphyrin complexes of metals such as iron, copper, and ruthenium.
The sensitizing dye layer 10d is formed by, for example, a method of immersing the porous semiconductor fine particle layer 10c in a sensitizing dye solution or a method of applying a sensitizing dye solution on the porous semiconductor fine particle layer 10c. Can be formed.

<Electrolyte layer>
The electrolyte layer 20 usually contains a supporting electrolyte, a redox couple (a pair of chemical species that can be reversibly converted into an oxidized form and a reduced form in a redox reaction), a solvent, and the like.

Here, examples of the supporting electrolyte include salts containing cations such as lithium ions, imidazolium ions, and quaternary ammonium ions.
As the redox pair, any compound capable of reducing the oxidized sensitizing dye may be used. Chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I ), Ruthenium ion (III) -ruthenium ion (II), copper ion (II) -copper ion (I), iron ion (III) -iron ion (II), cobalt ion (III) -cobalt ion (II), Examples include vanadium ion (III) -vanadium ion (II), manganate ion-permanganate ion, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid, and the like.
Furthermore, examples of the solvent include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N, N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate, and the like, which are solvents for forming an electrolyte layer of a solar cell. .

  The electrolyte layer 20 is prepared by applying a solution (electrolyte) containing the constituent components onto the photoelectrode 10 or manufacturing a cell having the photoelectrode 10 and the counter electrode 30 and injecting the electrolyte into the gap. It can be formed by doing.

(Solar cell module)
The solar cell module according to the present invention is obtained by connecting the above-described dye-sensitized solar cells in series and / or in parallel.
Here, in the solar cell module of the present invention, for example, the dye-sensitized solar cells according to the present invention are arranged on a flat surface or a curved surface, a non-conductive partition wall is provided between the cells, and the light of each battery is provided. It can be obtained by electrically connecting the electrode and the counter electrode using a conductive member.
And since the solar cell module which concerns on this invention uses the dye-sensitized solar cell which concerns on this invention, it is excellent in photoelectric conversion efficiency.
In addition, the number of the dye-sensitized solar cells used for forming the solar cell module is not particularly limited, and can be appropriately determined according to the target voltage.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In addition, the surface resistivity and bending resistance of the counter electrode layer films produced in Examples and Comparative Examples, and the conversion efficiency of the dye-sensitized solar cell element were evaluated using the following methods.

<Surface resistivity>
About the produced counter electrode layer film, according to JIS K7194, surface resistivity is measured by a four-terminal four-probe method using a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name “Loresta (registered trademark) GP”). Was measured.
<Flexibility>
The produced counter electrode layer film was cut into 50 mm × 150 mm to obtain a sample. Then, a silver paste (manufactured by Taiyo Ink Mfg. Co., Ltd., ECM-100 AF4820) is applied along both short sides of this sample in a range of 10 mm in width and 50 mm in length, and dried at a temperature of 90 ° C. for 30 minutes. An electrode was formed. A metal cylinder having a diameter of 5 mm is fixed to the center of the second carbon layer (catalyst layer) side of this sample, and the cylinder holding angle is measured along the cylinder from a holding angle of 0 ° (the sample is flat). Was bent 20 times within a range of 180 ° (a state where the sample was folded around a cylinder). When the resistance value between the terminal electrodes before bending is R0 and the resistance value between the terminal electrodes after bending is R, the resistance value change rate represented by R / R0 is used as an index of bending resistance. In addition, the resistance value between terminal electrodes was measured with the digital multimeter (the Kaise company make, KT-2011). And it judged on the following criteria.
R / R0 ≦ 10: ○ (good bending resistance)
R / R0> 10: × (Poor bending resistance)
<Conversion efficiency>
As a light source, a pseudo-sunlight irradiation device (PEC-L11 type, manufactured by Pexel Technologies, Inc.) in which an AM1.5G filter is attached to a 150 W xenon lamp light source was used. The amount of light was adjusted to 1 sun (AM1.5G, 100 mW / cm ² (JIS C8912 class A)). The produced dye-sensitized solar cell element was connected to a source meter (type 2400 source meter, manufactured by Keithley), and the following current-voltage characteristics were measured.
The output current was measured while changing the bias voltage from 0 V to 0.8 V in units of 0.01 V under 1 sun light irradiation. The output current was measured by integrating the values from 0.05 seconds to 0.15 seconds after changing the voltage in each voltage step. Measurement was also performed by changing the bias voltage from 0.8 V to 0 V in the reverse direction, and the average value of the measurements in the forward direction and the reverse direction was taken as the photocurrent.
In the measurement, in order to define the effective area of the dye-sensitized solar cell element, a black shading mask having a circular cutout portion having a diameter of 5.5 mm was used. An effective area was set to 0.2376 cm ² by placing a mask on the photoelectrode of the produced dye-sensitized solar cell element.
The photoelectric conversion efficiency (%) was calculated from the measurement result of the current-voltage characteristics.

Example 1
<Synthesis of carbon nanotubes>
SGCNTs were obtained by the super-growth method according to the description in WO 2006/011655.
The obtained SGCNT has a BET specific surface area of 804 m ² / g by nitrogen adsorption, a BET specific surface area of 2.4 m ² / g by water vapor adsorption, a mass density of 0.03 g / cm ³ , and a micropore volume of 0.44 mL / g. g. In addition, as a result of randomly measuring the diameter of 100 SGCNTs using a transmission electron microscope, the average diameter (Av) was 3.3 nm, and the sample standard deviation (σ) of the diameter was multiplied by 3 (3σ). Was 1.9 nm, (3σ / Av) was 0.58, and the average length was 100 μm. In addition, the obtained SGCNT was mainly composed of single-walled CNTs.
<Preparation of counter electrode for dye-sensitized solar cell>
In a sample bottle with a capacity of 30 mL, weigh 0.005 g of SGCNT as carbon 2 and 0.005 g of sodium salt (CMC) of carboxymethyl cellulose as dispersant 2, add 10 g of ion-exchanged water, and then add nitric acid. Was used to adjust the pH to 4. This was treated with a bath ultrasonic disperser for 30 minutes to obtain a carbon nanotube dispersion 2 (solution A).
Further, 0.020 g of SGCNT as carbon 1 and a copolymer of sodium styrenesulfonate (50) / disodium maleate (50) as dispersant 1 (molar ratio = 1 / First, 0.040 g of an average degree of polymerization of 50,000 and a number average molecular weight of 9,155,700) was weighed out, 8 mL of ion-exchanged water and 2 mL of ethanol were added, and then the pH was adjusted to 2 using 1N hydrochloric acid. This was subjected to a dispersion treatment with an ultrasonic homogenizer under ice-cooling (output 50 W, 120 minutes) to obtain a carbon nanotube dispersion 1 (solution B). In addition, the numerical value described in parentheses after each monomer name of the copolymer indicates the content ratio (mol%) of the monomer unit derived from the monomer in the copolymer. "Molar ratio" indicates the molar ratio of each monomer unit in the copolymer.
Next, the prepared solution B is a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., A4100, thickness 100 μm, A4 size) having a surface resin layer as a base material that serves as a support for the counter electrode. It was applied using a bar coater. The coating amount of SGCNT was 25 mg / ^{m 2.} The base material to which the solution B was applied was dried in a dryer at a temperature of 80 ° C. for 5 minutes.
Subsequently, the solution A was applied to the surface of the PET film on which the solution B was applied (on the film obtained by drying the solution B) using a bar coater. The coating amount of SGCNT was 10 mg / m ² . And the film which apply | coated the solution A is dried for 5 minutes at the temperature of 80 degreeC, the film (1st carbon layer) formed by drying the solution B, and the film (2nd carbon layer) formed by drying the solution A The laminate was formed on a PET film.
Thereafter, the laminate formed on the PET film was immersed in ion-exchanged water for 2 hours and then dried. Then, the laminated body was further subjected to UV treatment using a low-pressure mercury lamp for 15 minutes to substantially remove CMC from the second carbon layer. And the counter electrode for dye-sensitized solar cells formed by laminating | stacking the counter electrode layer film (laminated body after UV process) as a conductive laminated body on PET film was produced.
<Preparation of photoelectrode for dye-sensitized solar cell>
[Preparation of dye solution]
7.2 mg of ruthenium complex dye (N719, manufactured by Solaronics) was placed in a 20 mL volumetric flask. 10 mL of tert-butanol was added to the volumetric flask and stirred. Thereafter, 8 mL of acetonitrile was added, and the volumetric flask was stoppered, followed by stirring for 60 minutes by vibration with an ultrasonic cleaner. While keeping the solution at room temperature, acetonitrile was added to make the total volume 20 mL.
[Preparation of photoelectrode]
A low-temperature-deposited titanium oxide paste (manufactured by Pexel Technologies) is applied onto a substrate made of an ITO-PEN film, and the coating film is dried and then heated at a temperature of 150 ° C. for 10 minutes using a hot plate. A titanium oxide electrode was produced. This titanium oxide electrode was immersed in the N719 dye solution (0.3 mM). At this time, in order to perform sufficient dye adsorption, the dye solution was set to 2 mL or more per electrode.
The dye was adsorbed while keeping the dye solution at 40 ° C. Two hours later, the dye-adsorbed titanium oxide electrode was taken out of the petri dish, washed with an acetonitrile solution and dried to obtain a photoelectrode.
<Preparation of dye-sensitized solar cell element>
The inner side of a 25 μm thick heat-sealing film (manufactured by SOLARONIX) was cut into a circular shape having a diameter of 9 mm, and this film was set on the counter electrode. The electrolyte solution was dropped, the photoelectrodes were stacked from above, and both sides were sandwiched between worm clips to produce a dye-sensitized solar cell element. And conversion efficiency was evaluated. The results are shown in Table 1.

(Example 2)
When preparing the counter electrode for dye-sensitized solar cells, the counter electrode for dye-sensitized solar cells, dye-sensitized, except that the following solution C was used instead of solution A Type solar cell photoelectrode and dye-sensitized solar cell element were produced. And conversion efficiency was evaluated. The results are shown in Table 1.
[Preparation of Solution C]
In a sample bottle with a capacity of 50 mL, 0.005 g of SGCNT as carbon 2 and a 30% aqueous solution of sodium dodecyl diphenyloxide disulfonate as a dispersant 2 (product name “Dowfax (registered trademark) 2A1”, manufactured by Dow Chemical Co., Ltd.) 0 0.03 g was weighed and 10 g of ion-exchanged water was added. This was treated with a bath-type ultrasonic disperser for 30 minutes to obtain a carbon nanotube dispersion 2 (solution C).

(Comparative Example 1)
When producing a counter electrode for a dye-sensitized solar cell, the following solution D was used instead of solution A, and the laminate formed on the PET film was not immersed in ion-exchanged water and UV-treated. Then, a counter electrode layer film composed of a laminate of a film (first carbon layer) obtained by drying Solution B and a film (second carbon layer) obtained by drying Solution D is laminated on a PET film to increase the dye. A dye-sensitized solar cell photoelectrode and a dye-sensitized solar cell element were produced in the same manner as in Example 1 except that the counter electrode for the sensitive solar cell was used. And conversion efficiency was evaluated. The results are shown in Table 1.
[Preparation of Solution D]
A carbon nanotube dispersion (Solution D) was obtained in the same manner as Solution A except that the amount of sodium carboxymethylcellulose (CMC) as Dispersant 2 was 0.0115 g.

(Comparative Example 2)
A photoelectrode for dye-sensitized solar cell and a dye-sensitized solar cell element were prepared in the same manner as in Example 1 except that the counter electrode for dye-sensitized solar cell prepared as described below was used. And conversion efficiency was evaluated. The results are shown in Table 1.
<Preparation of counter electrode for dye-sensitized solar cell>
The solution A was applied onto the ITO surface of a polyethylene terephthalate (PET) film (ITO film thickness 200 nm, sheet resistance 15Ω / □) sputtered with indium-tin oxide (ITO) using a bar coater. The coating amount of SGCNT was 10 mg / m ² . And the film which apply | coated the solution A was dried for 5 minutes at the temperature of 100 degreeC, and the film formed by drying the solution A was formed on the ITO film | membrane of PET film.
Thereafter, a laminate formed by drying the ITO film and the solution A formed on the PET film was immersed in ion-exchanged water for 2 hours and then dried. Then, the laminate is further subjected to UV treatment using a low-pressure mercury lamp for 15 minutes, and a counter electrode layer film (laminated body after UV treatment) as a conductive laminate is laminated on the PET film. A counter electrode for a sensitive solar cell was produced.

  From Table 1, it can be seen that the counter electrode layer films of Examples 1 and 2 have low surface resistivity and excellent bending resistance (that is, excellent conductivity and mechanical properties). Moreover, it turns out that the dye-sensitized solar cell element of Examples 1-2 is excellent also in conversion efficiency (namely, it is excellent in electroconductivity and catalytic activity).

ADVANTAGE OF THE INVENTION According to this invention, the efficient manufacturing method of an electroconductive laminated body excellent in electroconductivity and desired activities, such as a catalyst activity, and this electroconductive laminated body can be provided.
Moreover, according to this invention, the counter electrode for dye-sensitized solar cells which is excellent in electroconductivity and catalytic activity can be provided.
Furthermore, according to this invention, the dye-sensitized solar cell and solar cell module which are excellent in photoelectric conversion efficiency can be provided.

DESCRIPTION OF SYMBOLS 10 Photoelectrode 30 Counter electrode 20 Electrolyte layer 10a, 30a Support body 10b, 30b Conductive layer 10c Porous semiconductor fine particle layer 10d Sensitizing dye layer 30c Catalyst layer 40 Circuit 100 Dye-sensitized solar cell

Claims (6)

A step (1) of forming a first carbon layer by applying a carbon dispersion 1 containing carbon 1, a dispersing agent 1 and a solvent 1 on a substrate and drying;
A step (2) of applying a carbon dispersion 2 containing carbon 2, a dispersant 2 and a solvent 2 on the first carbon layer obtained in step (1) and drying to form a second carbon layer;
At least the second carbon layer obtained in the step (2) is washed with the solvent 3, and at least a part of the dispersant 2 is removed from the second carbon layer, and / or
At least one treatment selected from the group consisting of plasma treatment, UV treatment and ozone treatment is performed on at least the second carbon layer obtained in step (2), and at least contained in the second carbon layer A decomposition step (4) for decomposing a part of the dispersant 2 that has been removed;
Only including,
At least one of the carbon 1 and the carbon 2 includes a carbon nanotube,
The carbon nanotube has a BET specific surface area of 600 m ² / g or more and 2600 m ² / g or less by nitrogen adsorption , and a BET specific surface area of 0.01 m ² / g or more and 30 m ² / g or less by water vapor adsorption. For producing a conductive laminate. The average length of the carbon nanotubes is 0.1μm or more 10mm or less, the production method of the electroconductive laminate according to claim 1. The manufacturing method of the conductive laminated body of Claim 1 or 2 whose surface resistivity of the said conductive laminated body is 0.01 ohm / square or more and 500 ohm / square or less. It is use the electroconductive laminate produced by the method for producing a conductive laminate according to any one of claims 1 to 3, the manufacturing method of the dye-sensitized solar cell for a counter electrode. Using a dye-sensitized solar cell for a counter electrode manufactured by the manufacturing method of the dye-sensitized solar cell for a counter electrode according to claim 4, the manufacturing method of the dye-sensitized solar cell. It includes connecting the dye-sensitized solar cell manufactured by the manufacturing method of the dye-sensitized solar cell of claim 5 in series and / or parallel, a method for manufacturing a solar cell module.

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