WO2020158507A1 - 分散液、導電膜およびその製造方法、電極、並びに、太陽電池 - Google Patents

分散液、導電膜およびその製造方法、電極、並びに、太陽電池 Download PDF

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WO2020158507A1
WO2020158507A1 PCT/JP2020/001921 JP2020001921W WO2020158507A1 WO 2020158507 A1 WO2020158507 A1 WO 2020158507A1 JP 2020001921 W JP2020001921 W JP 2020001921W WO 2020158507 A1 WO2020158507 A1 WO 2020158507A1
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conductive film
condensate
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solar cell
dispersion
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French (fr)
Japanese (ja)
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明彦 吉原
太田　龍史
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Zeon Corp
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Zeon Corp
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Priority to US17/424,163 priority Critical patent/US12162989B2/en
Priority to EP20749148.1A priority patent/EP3919560A4/en
Priority to CN202080009731.6A priority patent/CN113330066B/zh
Priority to JP2020569534A priority patent/JP7604895B2/ja
Publication of WO2020158507A1 publication Critical patent/WO2020158507A1/ja
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    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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    • H01—ELECTRIC ELEMENTS
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a dispersion, a conductive film and a method for manufacturing the same, an electrode, and a solar cell, and particularly to a dispersion, a conductive film obtained by using the dispersion and a method for manufacturing the same, an electrode including the conductive film, and , A solar cell provided with the electrode.
  • Carbon nanotubes (hereinafter sometimes referred to as “CNTs”), which is one of the carbon materials, are excellent in various properties such as electrical conductivity, thermal conductivity, mechanical strength, etc. Applications are under consideration. For example, a technique for forming a conductive film with CNT has been conventionally studied, paying attention to its excellent conductivity.
  • the conductive film containing CNTs is obtained by, for example, applying a carbon nanotube dispersion liquid (hereinafter, also referred to as “CNT dispersion liquid”) containing CNTs, a solvent, and a dispersant onto a base material, and then drying it. , Can be formed on a substrate. Then, in order to improve the performance of such a conductive film or a conductive film having a conductive film on a base material, attempts have been made to improve the dispersant used and the CNT dispersion liquid.
  • CNT dispersion liquid carbon nanotube dispersion liquid
  • Patent Document 1 a transparent conductive film including a conductive film made of CNT and an aromatic polymer as a dispersant, and a layer made of a resin layer on the conductive film, and having a specific light transmittance and surface resistivity, is provided. It has been reported that the conductive film has high durability, high conductivity, and excellent light transmittance.
  • an aqueous CNT dispersion liquid containing a dispersant having a number average molecular weight of 10,000 or more and 150,000 or less, such as a polysaccharide, at a specific ratio with respect to CNTs and having a pH adjusted within a specific range has been reported that while maintaining high dispersibility, it is excellent in stability against high shearing force.
  • Patent Document 3 a styrenesulfonic acid monomer residue, a maleimide residue having a substituted or unsubstituted aromatic hydrocarbon group on the nitrogen atom, and itaconic acid and fumaric acid each represented by a specific structural formula.
  • Polystyrene sulfonic acid copolymer containing another vinyl monomer residue derived from an acid or the like as a repeating structural unit, and the content ratio of each residue is 30 to 95 mol %, 5 to 70 mol %, and 0 to 20 mol %.
  • Patent Document 4 when dispersing CNT in a solvent, a sulfonic acid group-containing monomer unit is contained as a dispersant, and an ethylenically unsaturated aliphatic carboxylic acid monomer unit is contained in a specific ratio.
  • a polymer dispersant made of a polymer while suppressing the aggregation of CNTs in a CNT dispersion, it is possible to improve the adhesion between a conductive film formed using the dispersion and a substrate. It has been reported that it is possible.
  • a dispersion liquid such as a CNT dispersion liquid is required to have coating properties (wettability) with respect to a base material.
  • the conductive film formed from the dispersion liquid is required to have conductivity and excellent adhesion to the substrate. Further, for example, when the conductive film is used as a counter electrode of a dye-sensitized solar cell, excellent catalytic activity is required. In addition, a solar cell manufactured using a conductive film is required to have high conversion efficiency.
  • the coating property (wettability) of the dispersion liquid to the substrate and/or the adhesion between the conductive film formed from the dispersion liquid and the substrate are still insufficient. Therefore, there is room for improvement in the above-mentioned conventional technique in that the coating property (wettability) of the dispersion liquid with respect to the base material is improved while the adhesion of the conductive film formed from the dispersion liquid with the base material is improved. was there.
  • an object of the present invention is to provide a dispersion liquid capable of improving the coating property (wettability) with respect to a base material and forming a conductive film having high adhesion to the base material.
  • Another object of the present invention is to provide the conductive film, an electrode including the conductive film, and a solar cell including the electrode.
  • the dispersion liquid contains a carbon material (A), a condensate (B) of an aromatic sulfonic acid compound, a hydroxyphenol compound and an aldehyde compound, and a solvent (C), and The inventors have found that it is possible to improve the coating property (wettability) with respect to, and to form a conductive film having high adhesion to a substrate, and completed the present invention.
  • the present invention has an object to advantageously solve the above-mentioned problems, and the dispersion of the present invention comprises a carbon material (A), a condensation of an aromatic sulfonic acid compound, a hydroxyphenol compound and an aldehyde compound.
  • the product (B) and the solvent (C) are included.
  • the coating property (wettability) with respect to the substrate is improved.
  • a conductive film that can be improved and has high adhesion to a base material can be formed.
  • aromatic sulfonic acid compound means “a compound in which any one of hydrogen atoms in the aromatic compound is replaced with —SO 3 X (X is a hydrogen atom or a cation)”
  • Hydrophenol compound means “a compound having at least one hydroxy group (hydroxyl group)” and other than “aromatic sulfonic acid compound”.
  • the dispersion of the present invention comprises a hydroxyphenol compound monomer unit derived from a hydroxyphenol compound relative to an aromatic sulfonic acid compound monomer unit derived from an aromatic sulfonic acid compound in the condensate (B).
  • the molar ratio (hydroxyphenol compound monomer unit/aromatic sulfonic acid compound monomer unit) is preferably 1/9 or more and 9/1 or less.
  • the dispersibility of the condensate (B) can be improved.
  • a conductive film having high adhesion to the base material can be efficiently formed.
  • the dispersion of the present invention preferably has a weight average molecular weight (converted to standard polyethylene glycol) of the condensate (B) of 500 or more and 100,000 or less.
  • the weight average molecular weight (converted to standard polyethylene glycol) of the condensate (B) is 500 or more and 100,000 or less, the dispersibility of the carbon material can be improved and the coating property (wettability) on the substrate can be improved. it can.
  • a conductive film having high adhesion to the substrate can be efficiently formed, and a conductive film having improved conductivity, film strength, and catalytic activity when used as an electrode can be obtained.
  • a solar cell manufactured using this conductive film has high conversion efficiency.
  • the condensate (B) is preferably a resol type.
  • the condensate (B) is preferably represented by the following general formula (1) or the following general formula (2).
  • X represents a hydrogen atom or a cation
  • R 1 represents a hydroxyl group, —CH 2 —OH , or a group represented by the following general formula (3)
  • m, n, o and p are each an integer of 1 or more.
  • l is an integer of 0 to 4
  • Q is a divalent organic group
  • R 2 is a hydroxyl group, —CH 2 —OH, or a hydrogen atom.
  • Q in the general formula (3) is preferably a sulfonyl group.
  • the carbon material (A) is preferably a fibrous carbon nanostructure.
  • the solvent (C) contains water and the pH of the dispersion liquid is less than 7.
  • the dispersion of the present invention preferably contains 50 parts by mass or more and 500 parts by mass or less of the condensate (B) per 100 parts by mass of the carbon material (A).
  • the present invention has an object to advantageously solve the above problems, and the conductive film of the present invention is characterized by being obtained by using any one of the above-mentioned dispersion liquids.
  • the dispersion liquid of the present invention it is possible to provide a conductive film having excellent adhesion to a substrate.
  • an electrode of the present invention is characterized by including the above-mentioned conductive film.
  • the electrode provided with the conductive film of the present invention has excellent conductivity.
  • the present invention is intended to advantageously solve the above problems, and a solar cell of the present invention is characterized by including the above-mentioned electrode.
  • the solar cell provided with the electrode of the present invention has high conversion efficiency.
  • the present invention is intended to advantageously solve the above problems, the method for producing a conductive film of the present invention, any one of the above dispersion is applied to the substrate and dried to conduct A step (1) of forming a film, a step (2) of washing the conductive film obtained in the step (1) with a solvent to remove at least a part of the condensate (B) from the conductive film, It is characterized by including.
  • INDUSTRIAL APPLICABILITY The conductive film manufacturing method of the present invention can efficiently manufacture a conductive film having excellent adhesion to a substrate.
  • a dispersion liquid capable of improving the coating property (wettability) with respect to a substrate and forming a conductive film having high adhesion to the substrate.
  • a conductive film having high adhesion to a base material a method for producing the conductive film, an electrode having the conductive film and having high conductivity, and a solar cell having the electrode and having high conversion efficiency. Can be provided.
  • the carbon material dispersion liquid of the present invention contains the carbon material (A), the condensate (B), and the solvent (C), and further contains any other component as necessary.
  • the dispersion of the present invention is preferably acidic.
  • the dispersion liquid is acidic, when the dispersion liquid is applied on the conductive layer formed on the substrate, the conductive layer formed on the substrate and the dispersion liquid are eroded by the erosion of the conductive layer formed on the substrate. It is possible to improve the adhesion to the conductive layer.
  • the carbon material (A) is not particularly limited, and has conductivity, fibrous carbon nanostructure, graphene, fullerene, carbon nanohorn, graphite, activated carbon, carbon fiber, porous carbon, expanded graphite, carbon particles.
  • carbon black such as Ketjen black and acetylene black
  • the fibrous carbon nanostructure is preferable in that the conductive film obtained has excellent strength and catalytic performance.
  • the fibrous carbon nanostructure include a structure formed by stacking conical structures such as cup-stacked carbon nanotubes, and a cylindrical shape such as carbon nanobats and carbon nanotubes (CNTs).
  • a carbon nanostructure such as a carbon nanostructure or a non-cylindrical carbon nanostructure such as a graphene nanoribbon formed by forming a carbon six-membered ring network in a flat tubular shape can be used. These may be used alone or in combination of two or more.
  • a fibrous carbon nanostructure containing CNT as the fibrous carbon nanostructure.
  • the fibrous carbon nanostructure may be made of CNT only. If a fibrous carbon nanostructure containing CNTs is used, even if the compounding amount is small, the obtained conductive film can have properties such as conductivity, film strength, and catalytic activity when used for a solar cell electrode. This is because it can be efficiently given.
  • CNTs in the fibrous carbon nanostructure are not particularly limited, and single-walled carbon nanotubes and/or multi-walled carbon nanotubes can be used.
  • the CNTs are preferably single-walled to five-walled carbon nanotubes, and more preferably single-walled carbon nanotubes. These may be used alone or in combination of two or more.
  • the average diameter of the fibrous carbon nanostructures is preferably 1 nm or more, preferably 60 nm or less, more preferably 30 nm or less, and particularly preferably 10 nm or less.
  • the average diameter of the fibrous carbon nanostructures is 1 nm or more, the dispersibility of the fibrous carbon nanostructures can be enhanced and the conductive film can be stably imparted with favorable characteristics such as conductivity.
  • the average diameter of the fibrous carbon nanostructures is 60 nm or less, even if the compounding amount is small, the obtained conductive film can efficiently exhibit characteristics such as catalytic activity when used in a solar cell electrode. Can be given to.
  • the “average diameter of fibrous carbon nanostructures” is, for example, the diameter (outer diameter) of 20 fibrous carbon nanostructures measured on a transmission electron microscope (TEM) image. , Can be obtained by calculating the number average value.
  • the fibrous carbon nanostructure the ratio (3 ⁇ /Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ : sample standard deviation) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20.
  • a fibrous carbon nanostructure of less than 0.60 is preferably used, and a fibrous carbon nanostructure of 3 ⁇ /Av of more than 0.25 is more preferably used, and a fibrous carbon of 3 ⁇ /Av of more than 0.40 is used. It is particularly preferred to use carbon nanostructures.
  • the use of the fibrous carbon nanostructure having 3 ⁇ /Av of more than 0.20 and less than 0.60 can further improve the performance of the produced conductive film.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the fibrous carbon nanostructure may be adjusted by changing the production method or production conditions of the fibrous carbon nanostructure, or obtained by a different production method.
  • the fibrous carbon nanostructure may be adjusted by combining a plurality of types.
  • the fibrous carbon nanostructure it is usually used that the diameter measured as described above is plotted on the abscissa and the frequency is plotted on the ordinate, and a normal distribution is obtained when approximated by Gaussian. To be done.
  • the average length of the fibrous carbon nanostructure is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, particularly preferably 80 ⁇ m or more, and preferably 600 ⁇ m or less, 500 ⁇ m It is more preferably not more than 400 ⁇ m, particularly preferably not more than 400 ⁇ m.
  • the average length is 10 ⁇ m or more, a conductive path can be formed in the conductive film with a small amount and the strength of the conductive film is high.
  • the average length is 600 ⁇ m or less, the coating property on the base material can be improved when the dispersion liquid is coated.
  • the average length of the fibrous carbon nanostructures is, for example, the length of 20 fibrous carbon nanostructures measured on a scanning electron microscope (SEM) image. It can be obtained by calculating the average value.
  • the fibrous carbon nanostructure usually has an aspect ratio of more than 10.
  • the aspect ratio of the fibrous carbon nanostructures was determined by measuring the diameter and length of 100 randomly selected fibrous carbon nanostructures using a scanning electron microscope or a transmission electron microscope. It can be determined by calculating the average value of the ratio to the length (length/diameter).
  • the fibrous carbon nanostructure has a BET specific surface area of preferably 200 m 2 /g or more, more preferably 400 m 2 /g or more, particularly preferably 600 m 2 /g or more, It is preferably 2000 m 2 /g or less, more preferably 1800 m 2 /g or less, and particularly preferably 1600 m 2 /g or less.
  • the BET specific surface area of the fibrous carbon nanostructures is 200 m 2 /g or more, the dispersibility of the fibrous carbon nanostructures is increased, and the conductive film and the solar cell with respect to the conductive film obtained can be obtained with a small amount. It is possible to satisfactorily impart characteristics such as catalytic activity when used as a working electrode.
  • BET specific surface area of the fibrous carbon nanostructure is 2000 m 2 /g or less
  • the obtained conductive film is satisfactorily imparted with properties such as conductivity and catalytic activity when used as a solar cell electrode.
  • the coating property of the dispersion liquid can be stabilized.
  • BET specific surface area refers to the nitrogen adsorption specific surface area measured using the BET method.
  • the fibrous carbon nanostructure preferably has a t-plot obtained from the adsorption isotherm showing a convex shape.
  • the “t-plot” is obtained by converting the relative pressure into the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm of the fibrous carbon nanostructure measured by the nitrogen gas adsorption method. You can That is, from the known standard isotherm obtained by plotting the average thickness t of the nitrogen gas adsorption layer against the relative pressure P/P0, obtain the average thickness t of the nitrogen gas adsorption layer corresponding to the relative pressure and perform the above conversion. Gives a t-plot of the fibrous carbon nanostructure (t-plot method by de Boer et al.).
  • the t-plot showing the upward convex shape is located on a straight line passing through the origin in the region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t becomes large, the plot becomes the straight line. The position is shifted downward from.
  • the fibrous carbon nanostructure having the shape of the t-plot has a large ratio of the internal specific surface area to the total specific surface area of the fibrous carbon nanostructure, and many carbon nanostructures constituting the fibrous carbon nanostructure. Indicates that an opening is formed.
  • the bending point of the t-plot of the fibrous carbon nanostructure is preferably in the range of 0.2 ⁇ t(nm) ⁇ 1.5, and 0.45 ⁇ t(nm) ⁇ 1.5. Is more preferable, and 0.55 ⁇ t(nm) ⁇ 1.0 is particularly preferable.
  • the inflection point of the t-plot of the fibrous carbon nanostructure is within such a range, the dispersibility of the fibrous carbon nanostructure can be enhanced, and the properties such as conductivity of the conductive film can be enhanced with a small amount of compounding. ..
  • the fibrous carbon nanostructures are likely to aggregate and the dispersibility decreases, and if the value of the bending point exceeds 1.5, the fibrous carbon nanostructure is formed.
  • the structures may be easily entangled with each other and the dispersibility may be reduced.
  • the "position of the bending point" is the intersection of the approximate straight line A in the above process (1) and the approximate straight line B in the above process (3).
  • the ratio (S2/S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot is preferably 0.05 or more and 0.30 or less.
  • the dispersibility of the fibrous carbon nanostructure can be enhanced and the properties such as the conductivity of the conductive film can be enhanced with a small blending amount.
  • the total specific surface area S1 and the internal specific surface area S2 of the fibrous carbon nanostructure can be obtained from its t-plot.
  • the total specific surface area S1 can be obtained from the slope of the approximate straight line in the process (1), and the external specific surface area S3 can be obtained from the slope of the approximate straight line in the process (3). Then, the internal specific surface area S2 can be calculated by subtracting the external specific surface area S3 from the total specific surface area S1.
  • the measurement of the adsorption isotherm of the fibrous carbon nanostructure, the preparation of the t-plot, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-plot are carried out by using, for example, a commercially available measuring device.
  • "BELSORP (registered trademark)-mini” manufactured by Nippon Bell Co., Ltd.
  • the fibrous carbon nanostructure containing CNT suitable as the fibrous carbon nanostructure has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. It should be noted that RBM does not exist in the Raman spectrum of the fibrous carbon nanostructure composed of only multi-walled carbon nanotubes having three or more layers.
  • the ratio of the G band peak intensity to the D band peak intensity (G/D ratio) in the Raman spectrum is preferably 0.5 or more and 10.0 or less, and 1 It is more preferably from 0.0 to 5.0.
  • G/D ratio is 0.5 or more and 10.0 or less, characteristics such as catalytic activity when used for a solar cell electrode can be favorably imparted to the obtained conductive film.
  • the fibrous carbon nanostructure containing CNTs preferably has an oxygen atom amount of 5 atom% or less, and preferably 2 atom% or less, based on the total of carbon atoms and oxygen atoms by XPS elemental analysis. More preferably, it is particularly preferably 1 atomic% or less. When the amount of oxygen atoms is within the preferable range, it is possible to favorably provide the obtained conductive film with properties such as catalytic activity when used in a solar cell electrode.
  • the proportion of carbon atoms is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass or more by elemental analysis of CHN. More preferably, it is particularly preferably 98 mass% or more, the proportion of hydrogen atoms is preferably 1 mass% or less, more preferably 0.8 mass% or less, 0.3 mass% The content is more preferably the following or less, and particularly preferably 0.1% by mass or less.
  • the ratio of carbon atoms (hydrogen atoms) is within the preferable range, it is possible to satisfactorily provide the obtained conductive film with properties such as catalytic activity when used for a solar cell electrode.
  • the fibrous carbon nanostructure containing CNTs is not particularly limited, and is manufactured using a known CNT synthesis method such as an arc discharge method, a laser ablation method, or a chemical vapor deposition method (CVD method). can do.
  • a fibrous carbon nanostructure containing CNTs is prepared by, for example, supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for producing carbon nanotubes on the surface thereof and performing chemical vapor deposition (CVD). Method), by which a small amount of an oxidizing agent (catalyst activating substance) is present in the system when CNTs are synthesized by the method (super growth method; WO 2006). /011655), and can be efficiently produced.
  • the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.
  • the fibrous carbon nanostructure manufactured by the super growth method may be composed of only SGCNT, or in addition to SGCNT, for example, another carbon nanostructure such as a non-cylindrical carbon nanostructure. May be included.
  • the content of the carbon material (A) in the dispersion is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and 0 in the entire dispersion. 0.1 mass% or more is particularly preferable, 30.0 mass% or less is preferable, 10.0 mass% or less is more preferable, 5.0 mass% or less is further preferable, It is particularly preferably 1.0% by mass or less.
  • the condensate (B) is a condensate of an aromatic sulfonic acid compound, a hydroxyphenol compound and an aldehyde compound, and functions as a dispersant for the carbon material (A). Since the condensate (B) has excellent dispersibility of the carbon material (A) such as CNT and is easily removed by washing with a solvent, the catalytic activity is improved, the adhesion is high, and the strength of the film itself is high. A film can be obtained, and thus an excellent electrode such as a counter electrode can be obtained.
  • Aromatic sulfonic acid compound means “a compound in which any of hydrogen atoms in an aromatic compound is replaced by —SO 3 X (X is a hydrogen atom or a cation)”.
  • aromatic sulfonic acid compound include phenolsulfonic acid (PSA) such as p-phenolsulfonic acid, o-phenolsulfonic acid and phenoldisulfonic acid; 1-naphthol-4-sulfonic acid, 2-naphthol-6-sulfone.
  • Hydroxyphenol compound means "a compound having at least one hydroxy group (hydroxyl group)" and other than "aromatic sulfonic acid compound".
  • hydroxyphenol compound include hydroxy such as bisphenol A, 4,4-biphenol, 3,3,5,5-tetramethyl-4,4-biphenol, and bis(4-hydroxy-3,5-dimethylphenyl)methane.
  • Phenol those having a naphthalene skeleton such as 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,1-bis(2-naphthol); 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl Hydroxydiphenylsulfone (BS) such as sulfone and bis(4-hydroxy-3,5-dimethylphenyl)sulfone; 1,1,1-tris(4-hydroxyphenyl)methane, 1,1,2,2,-tetrakis And polyfunctional phenols such as (4-hydroxyphenyl)ethane; and the like.
  • BS 2,4'-dihydroxydiphenyl Hydroxydiphenylsulfone
  • BS 2,4'-dihydroxydiphenyl Hydroxydiphenylsulfone
  • 1,1,1-tris(4-hydroxyphenyl)methane 1,1,2,2,-tetra
  • These may be used individually by 1 type and may be used in combination of 2 or more types by arbitrary ratios.
  • adhesion to a base material, and solubility of the resulting condensate in a solvent it has 2 to 4 hydroxyl groups such as dihydroxydiphenyl sulfone and has a 6-membered ring.
  • a compound having 1 or more and 3 or less and a linking group such as a sulfonyl group is preferable.
  • aldehyde compound examples include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and glyoxal; aldehydes having a cyclic structure such as furfural, benzaldehyde, salicylaldehyde, and paraformaldehyde; An aqueous solution may be used as the aldehyde compound.
  • aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, and glyoxal
  • aldehydes having a cyclic structure such as furfural, benzaldehyde, salicylaldehyde, and paraformaldehyde
  • An aqueous solution may be used as the aldeh
  • the aldehyde compound is preferably used in an amount of 0.5 times or more and 2 times or less, and 1.0 times or more and 1.9 times the total amount of the aromatic sulfonic acid compound and the hydroxyphenol compound used. It is more preferable to use about a molar amount or less. When it is at least the above lower limit, a large amount of unreacted aromatic sulfonic acid compound and hydroxyphenol compound at the end of the reaction can be suppressed, and when it is at most the above upper limit, the free aldehyde compound in the condensate liquid Can be suppressed.
  • the condensation reaction of the aromatic sulfonic acid compound, the hydroxyphenol compound and the aldehyde compound is performed by a known method.
  • an aromatic sulfonic acid compound, a hydroxyphenol compound and an aldehyde compound are subjected to a condensation reaction under an acid catalyst or an alkali catalyst to produce an aldehyde condensate (condensate (B)).
  • condensation reaction of the aromatic sulfonic acid compound, the hydroxyphenol compound and the aldehyde compound is performed, water, alcohol or the like is used as a solvent.
  • Examples of the acid catalyst include hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, toluenesulfonic acid, and the like. These may be used individually by 1 type and may be used in combination of 2 or more types by arbitrary ratios.
  • Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; amines such as ammonia and triethylamine; To be These may be used individually by 1 type and may be used in combination of 2 or more types by arbitrary ratios. Among these, sodium hydroxide is preferable from the viewpoint of easy operation.
  • an acid catalyst may be selected when a novolac type is prepared, and an alkali catalyst is selected when a resol type is prepared.
  • an aromatic sulfonic acid compound a hydroxyphenol compound and an aldehyde compound in the presence of an alkali catalyst
  • the amount of alkali necessary to neutralize the strongly acidic component present in the reaction system is used. ..
  • the strongly acidic component present in the reaction system include free sulfuric acid and sulfonic acid groups bonded to phenols.
  • the reaction temperature and the reaction time are not particularly limited, and the reaction temperature and the reaction that facilitate the production of the condensate (B) having a desired weight average molecular weight (standard polyethylene glycol conversion) from the viewpoint of management.
  • the time may be selected appropriately.
  • the reaction temperature is not particularly limited, but it is preferably 60° C. or higher, and preferably 120° C. or lower.
  • the reaction time is not particularly limited, but is preferably 3 hours or longer, and preferably 20 hours or shorter.
  • the obtained formaldehyde condensate may be isolated after the condensation reaction, or the reaction product may be used as it is.
  • the structure of the condensate (B) includes, for example, novolak type (thermoplastic type) such as random novolac and high ortho novolac, and resol type (thermosetting type) such as benzyl ether resole, ammonia resole, and alkali resole.
  • novolak type thermoplastic type
  • resol type thermosetting type
  • the condensate (B) preferably has a structure of the resol type, and has the following general formula (1) Or more preferably represented by the following general formula (2).
  • X is a hydrogen atom or a cation
  • R 1 is a hydroxyl group, —CH 2 —OH, or a group represented by the following general formula (3)
  • m, n, o, and p are each an integer of 1 or more, preferably an integer of 1 ⁇ m ⁇ 235, an integer of 1 ⁇ n ⁇ 206, an integer of 1 ⁇ o ⁇ 192, and 1 ⁇ p ⁇ It is an integer of 206.
  • l is an integer of 0 to 4
  • R 2 is a hydroxyl group, —CH 2 —OH, or a hydrogen atom.
  • the cation as X in the general formula (1) includes, for example, lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion, ammonium ion and the like.
  • the molar ratio of the hydroxyphenol compound monomer unit derived from the hydroxyphenol compound to the aromatic sulfonic acid compound monomer unit derived from the aromatic sulfonic acid compound is preferably 1/9 or more, more preferably 1/5 or more, further preferably 1/4 or more, and 1/3 or more. It is particularly preferable that it is 9/1 or less, more preferably 5/1 or less, still more preferably 4/1 or less, and particularly preferably 3/1 or less.
  • the solubility of the condensate (B) in the solvent (C) can be improved, and a conductive film having high adhesion to the substrate can be formed.
  • the dispersibility of the carbon material (A) can be improved.
  • the weight average molecular weight (calculated as standard polyethylene glycol) of the condensate (B) is preferably 500 or more, more preferably 1,000 or more, further preferably 2,000 or more, and 5,000. It is particularly preferable that it is not less than 100, preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less.
  • the weight-average molecular weight (converted to standard polyethylene glycol) of the condensate (B) is at least the above lower limit, sufficient adhesion to the substrate and film strength can be imparted to the obtained conductive film.
  • it is at most the above upper limit the dispersibility of the carbon material, the rinsing property of the obtained conductive film, and the electrode performance of the obtained electrode will be excellent.
  • the content of the condensate (B) per 100 parts by mass of the carbon material (A) is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and particularly preferably 130 parts by mass or more. It is preferably 500 parts by mass or less, more preferably 350 parts by mass or less, and particularly preferably 250 parts by mass or less.
  • the content is at least the above lower limit, it is possible to sufficiently impart the adhesiveness to the substrate and the film strength to the obtained conductive film, and when it is at most the above upper limit, the dispersion of the carbon material is achieved. , Excellent rinsing properties and electrode performance of the obtained electrode.
  • the solvent (C) may be an aqueous solvent or an organic solvent solvent, but it is preferable to use an aqueous solvent (that is, the solvent (C) preferably contains water).
  • the aqueous solvent is not particularly limited as long as the carbon material (A) such as CNT can be dispersed therein, and water may be used alone, or a mixed solvent of solvents miscible with water. May be used.
  • ethers dioxane, tetrahydrofuran, methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol butyl ether, etc.
  • ether alcohols ethoxyethanol, methoxyethoxyethanol, etc.
  • esters methyl acetate, ethyl acetate, etc.
  • Ketones acetone, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, etc.
  • alcohols methanol, ethanol, isopropanol, propylene glycol, ethylene glycol, diacetone alcohol, phenol, etc.
  • lower carboxylic acids acetic acid, etc.
  • amines examples thereof include triethylamine, trimethanolamine and the like), nitrogen-containing polar solvents (N,N-dimethylformamide, nitromethane, N-methylpyrrolidone, acetonitrile and the
  • ethers, ketones, and alcohols are preferable as the solvent miscible with water, from the viewpoint of improving the stability of the dispersion liquid. These may be deaerated and the like at appropriate times.
  • the pH of the dispersion liquid is not particularly limited, but is preferably 0.1 or higher, more preferably 0.2 or higher, and 0.5 or higher. It is particularly preferable that it is less than 7, that is, it is acidic, more preferably 6 or less, still more preferably 5 or less, even more preferably 4 or less, and 2.5 or less. Is particularly preferable.
  • An acidic substance may be added to lower the pH of the dispersion liquid.
  • the acidic substance for example, sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, tartaric acid, formic acid, phosphoric acid and the like are preferable, and hydrochloric acid and nitric acid are more preferable from the viewpoint of easy rinse removal.
  • ⁇ Other ingredients> include inorganic materials such as silica, metal particles, binders, conductive aids, surfactants, defoamers, antiaging agents, preservatives and the like. Known materials may be appropriately used as these. One kind may be used alone, and two kinds or more may be used in combination at an arbitrary ratio.
  • the method for producing the dispersion is not particularly limited, but the condensate (B)-containing solution obtained by dissolving the condensate (B) that functions as a dispersant in a solvent is used as a carbon material (A) and a solvent (C). ), and the carbon material (A) may be added to the mixture of the condensate (B) and the solvent (C).
  • the condensate (B)-containing alkaline aqueous solution obtained by dissolving the condensate (B) that functions as a dispersant in a good solvent is used as a carbon material (A) and a solvent (C) (for example, an acidic aqueous solution). ) May be added to the mixture.
  • a known method can be used for the mixing treatment and the dispersion treatment of the dispersion liquid.
  • a method using a wet jet mill such as a nanomizer or an optimizer, a high pressure homogenizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a homomixer, or the like.
  • a wet jet mill such as a nanomizer or an optimizer, a high pressure homogenizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a homomixer, or the like.
  • these may be used alone or in combination of two or more.
  • a high-pressure homogenizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a homomixer, or other high-speed agitator is used as the preliminary dispersion, and a main atomizer such as a nanomizer or an optimizer is used as the main dispersion.
  • a main atomizer such as a nanomizer or an optimizer is used as the main dispersion.
  • the temperature at the time of dispersion is not particularly limited, but is usually not more than the boiling point of the solvent, preferably not more than 60°C, more preferably not more than 40°C, preferably not less than -10°C, more preferably not less than 0°C.
  • the solubility and structure of the dispersant can be controlled, and the dispersibility of the carbon material (A) can be improved. For example, even when treated in an acidic solution, the carbon material ( The deterioration of A) can be suppressed.
  • the conductive film of the present invention is formed using the above-mentioned dispersion liquid. Since the conductive film of the present invention contains the carbon material (A) that is well dispersed, it has excellent conductivity and mechanical properties. Such a conductive film is excellent in adhesiveness (adhesiveness) with a substrate and catalytic activity.
  • the conductive film of the present invention is suitably used, for example, as a conductive film of a photoelectrode substrate or a counter electrode (catalyst electrode) substrate or a catalyst layer of a counter electrode (catalyst electrode) described later. Particularly, it is preferably used as a catalyst layer of a counter electrode (catalyst electrode).
  • the method for producing a conductive film of the present invention comprises a step (1) of applying the dispersion of the present invention onto a substrate and drying it to form a conductive film, and washing the conductive film obtained in the step (1) with a solvent.
  • the method further includes the step (3) of decomposing.
  • Step (1) the dispersion liquid of the present invention is applied onto a substrate, and the applied dispersion liquid is dried to form a conductive film.
  • the base material can be coated with the above-mentioned dispersion liquid, and the shape, the constituent material, and the size (thickness, etc.) are not particularly limited as long as the obtained conductive film can be supported, and are appropriately selected depending on the intended use. can do.
  • the base material a base material on which a known conductive film other than the conductive film of the present invention is formed, a base material provided with an undercoat layer of resin or the like, an organic/inorganic barrier layer having a barrier property against oxygen and moisture. You may use the base material which has.
  • a known application method can be adopted.
  • 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, inkjet method, spraying method and the like can be mentioned. ..
  • the screen printing method is preferable because it is easy to form the electrode pattern.
  • the coating may be carried out not only once but also as many times as necessary, and two different coating methods may be combined.
  • the coating thickness (wet thickness) at the time of applying the dispersion of the present invention onto a substrate is not particularly limited as long as the conductivity of the obtained film is secured, but is preferably 0.001 ⁇ m or more, and 0 It is more preferably 0.005 ⁇ m or more, particularly preferably 0.01 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the coating amount of CNT per unit area of the base material when the dispersion liquid of the present invention is applied onto the base material is preferably 0.001 mg/m 2 or more, and 0.005 mg/m 2 More preferably, it is more preferably 0.01 mg/m 2 or more, particularly preferably 50 g/m 2 or less, more preferably 10 g/m 2 or less, and 3 g/m 2 or less. Is particularly preferable.
  • the type (shape) and thickness of the carbon material used are usually reflected in the conductive film obtained as it is. Therefore, the thickness of the conductive film of the present invention is not particularly limited, but is usually 100 nm to 1 mm.
  • the thickness of the conductive film is usually 0.01 ⁇ m to 100 ⁇ m, preferably 0.1 ⁇ m to It is 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m.
  • the conductivity as an electrode and the catalytic performance are excellent, and when a module is formed, the overall series resistance and the like are excellent in balance.
  • the conductivity becomes more excellent.
  • the conductive film of the present invention has excellent conductivity.
  • the sheet resistance of the conductive film of the present invention is usually 0.01 ⁇ / ⁇ to 1000 ⁇ / ⁇ , preferably 0.1 ⁇ / ⁇ to 100 ⁇ / ⁇ , and more preferably 0.5 to 20 ⁇ / ⁇ .
  • the surface resistivity of this conductive film is measured by a method according to JIS K7194 using a low resistivity meter (for example, product name “Loresta (registered trademark)-GP MCP-T610” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Can be measured.
  • a known drying method can be adopted. For example, by air drying method, heat drying method such as hot roll drying method, reduced pressure drying method, infrared irradiation method, light irradiation method using xenon lamp, flash lamp, etc., electromagnetic wave heating method using microwave etc. Then, the dispersion liquid on the base material is dried to form a conductive film on the base material.
  • the drying temperature is not particularly limited as long as the solvent (C) can be removed by vaporization and is lower than the heat resistant temperature of the substrate.
  • the drying temperature is preferably 0°C or higher, more preferably 15°C or higher, even more preferably room temperature or higher, particularly preferably 80°C or higher, and preferably 250°C or lower. It is more preferably 200° C. or lower, particularly preferably 150° C. or lower.
  • the drying time is not particularly limited, but it is preferably 0.1 minutes or longer, and preferably 150 minutes or shorter.
  • the drying atmosphere is not particularly limited, such as a humidified atmosphere, the atmosphere, an inert gas such as nitrogen or argon, or a reduced pressure such as a vacuum.
  • step (2) is performed after the step (1). From the viewpoint of more efficiently removing the condensate (B) (dispersant) from the conductive film, it is preferable to perform both step (2) and step (3).
  • step (2) the conductive film obtained in step (1) is washed with a solvent to remove at least part of the condensate (B) (dispersant) from the conductive film.
  • the cleaning may be performed on the conductive film obtained in step (1), for example.
  • the conductive film and a solvent capable of dissolving the condensate (B) are brought into contact with each other, and the condensate (B) in the conductive film is eluted into the solvent to remove one of the condensate (B) in the conductive film. Part is removed from the conductive film.
  • the solvent capable of dissolving the condensate (B) is not particularly limited, and the same solvent as the solvent (C) can be used. Among them, water, alcohols, ketones, nitrogen-containing polar solvents and the like are preferable, and alkaline aqueous solutions are more preferable, from the viewpoint of easy handling.
  • the cleaning of the conductive film using the solvent capable of dissolving the condensate (B) described above can be performed by, for example, immersing the conductive film in the solvent or applying the solvent to the conductive film.
  • cleaning of the conductive film may be performed plural times.
  • the conductive film after cleaning can be dried by using a known method.
  • the immersion time is preferably 30 seconds or longer, more preferably 1 minute or longer, and further preferably 3 minutes or longer. Is particularly preferable, it is preferably 1 hour or less, and more preferably 30 minutes or less. This is because the condensate (B) can be sufficiently removed by setting the immersion time to 30 seconds or more. Further, if the immersion time is set to 1 hour or less, it is possible to prevent the carbon material from falling off from the conductive film and the conductive film from peeling off from the base material due to excessive cleaning.
  • Step (3) at least one treatment selected from the group consisting of plasma treatment, UV treatment, and ozone treatment (hereinafter referred to as “decomposition treatment”) on at least the conductive film obtained in step (1). Is performed) to decompose at least part of the condensate (B) contained in the conductive film.
  • the order of the steps is not particularly limited, but the conductive film that has been washed in the step (2) is decomposed in the step (3). Is preferred. That is, when both step (2) and step (3) are performed, it is preferable that the condensate (B) remaining in the conductive film after the washing in step (2) is decomposed in step (3). ..
  • the decomposition treatment may be performed on the conductive film, for example.
  • at least one treatment selected from the group consisting of plasma treatment, UV treatment, and ozone treatment is performed on the conductive film, whereby at least the condensate (B ) Part of.
  • a decomposed product generated during the decomposition treatment may be optionally removed by a technique such as washing after the decomposition treatment. From the viewpoint of ease of treatment, it is preferable to use UV treatment as the decomposition treatment.
  • the amount of the condensate (B) (dispersing agent) in the conductive film is reduced and the carbon content in the conductive film is improved.
  • a long CNT such as SGCNT is used as A
  • the CNTs are entangled with each other to form a network structure, even if the condensate (B) (dispersant) is removed, the layer shape is changed. Can be maintained well.
  • the cleaning and decomposition treatment may be performed on the conductive film formed on the base material or may be performed on the conductive film separated from the base material.
  • the cleaning and/or decomposition treatment described above reduces the content ratio of the condensate (B) (dispersant) contained in the conductive film, while it is contained in the conductive film.
  • the carbon content ratio increases.
  • the condensate (B) (dispersing agent) existing on the surface of the conductive film is removed, and more carbon is exposed on the surface of the conductive film. Therefore, the catalytic activity of the conductive film is improved.
  • the electrode of the present invention is obtained by using the conductive film of the present invention.
  • the electrode of the present invention is suitably used for an organic solar cell such as a dye-sensitized solar cell (DSC), an organic thin film solar cell, and a perovskite solar cell.
  • DSC dye-sensitized solar cell
  • the electrode of the present invention will be described by taking DSC as an example.
  • the DSC usually has a structure in which a photoelectrode, an electrolyte layer, and a counter electrode are arranged in this order.
  • the photoelectrode is an electrode that can emit electrons to an external circuit by receiving light.
  • the photoelectrode is usually a photoelectrode substrate having a conductive film formed on a base material, a porous semiconductor fine particle layer formed on the photoelectrode substrate, and a sensitizing dye on the surface of the porous semiconductor fine particle layer. And a sensitizing dye layer formed by adsorption.
  • the electrolyte layer is a layer for separating the photoelectrode and the counter electrode and efficiently performing charge transfer.
  • the counter electrode is an electrode for efficiently passing electrons that have entered from an external circuit to the electrolyte layer.
  • the counter electrode usually has a counter electrode substrate having a conductive film formed on a base material, and a catalyst layer formed on the counter electrode substrate.
  • the photoelectrode is usually composed of a photoelectrode substrate having a conductive film of the present invention formed on a substrate, a porous semiconductor fine particle layer formed on the photoelectrode substrate, and a porous semiconductor fine particle layer. And a sensitizing dye layer formed by adsorbing a sensitizing dye on the surface.
  • the base material is not particularly limited in shape, constituent material, and size (thickness, etc.) as long as the dispersion liquid of the present invention can be applied on the base material and the resulting conductive film can be supported. You can choose.
  • the materials forming the base material examples of the inorganic material include metals such as titanium, stainless steel, aluminum, iron, gold and silver, and glass.
  • examples of organic materials include carbon materials and plastic substrate materials.
  • a plastic substrate material is preferable from the viewpoint of improving the adhesion (adhesiveness) to the conductive film, and the stretchability and flexibility of the conductive film. Further, as the plastic substrate material, a material having high heat resistance, excellent chemical resistance and gas barrier property, and low cost is preferable.
  • plastic substrate material may be non-colored and transparent.
  • plastic substrate materials include polyesters (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), styrenes (syndiotactic polystyrene (SPS), etc.), polyphenylene sulfide (PPS), etc. , Polycarbonate (PC), Polyarylate (PAr), Polysulfone (PSF), Polyester sulfone (PES), Polyetherimide (PEI), Transparent polyimide (PI), Cycloolefin copolymer (trade name "Arton” (registered trademark), etc.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS styrenes
  • PPS polyphenylene sulfide
  • PC Polycarbonate
  • PAr Polyarylate
  • PSF Polysulfone
  • PET Polyetherimide
  • PI Transparent polyimide
  • PI Cycloolef
  • alicyclic polyolefin (trade name “Zeonor” (registered trademark), etc.), polycarbonate, polyamide, polyurethane, polymethylmethacrylate, cellulose, triacetylcellulose, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, alicyclic Formula acrylic resin, etc. are used.
  • polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and alicyclic polyolefin are particularly preferable from the viewpoint of chemical stability and cost.
  • the preferable thickness of the base material is not particularly limited and can range from a moderate thickness to a very thin thickness.
  • the thickness of the base material is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably 20 ⁇ m or more, preferably 1000 ⁇ m or less, and more preferably 500 ⁇ m or less.
  • the thickness is preferably 250 ⁇ m or less, and particularly preferably 250 ⁇ m or less.
  • a base material on which a known conductive film other than the conductive film of the present invention is formed, or a base material provided with an undercoat layer such as resin may be used as the base material.
  • the known conductive film include metals such as platinum, gold, silver, copper, aluminum, indium, and titanium; conductive metal oxides such as tin oxide and zinc oxide; indium-tin oxide (ITO) and indium.
  • -Composite metal oxides such as zinc oxide (IZO) and fluorine-doped tin oxide (FTO); carbon materials such as carbon nanotubes, carbon nanobats, graphene, fullerenes, diamond-like carbon (DLC); and two or more of these. Examples include combinations.
  • the thickness thereof is not particularly limited, it is usually 0.001 ⁇ m or more, preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more and 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 1 ⁇ m or less, further preferably 0.1 ⁇ m or less. It is 5 ⁇ m or less.
  • the substrate may be subjected to surface hydrophilic treatment such as glow discharge treatment, corona discharge treatment or UV ozone treatment on the surface on which the dispersion liquid of the present invention is applied or the surface on which a porous semiconductor fine particle layer described below is formed. .. Further, abrasion resistance, high surface hardness, solvent resistance, stain resistance, fingerprint resistance, antireflection property, etc. were imparted to the surface of the base material on which the dispersion of the present invention is applied or the surface opposite thereto. A hard coat treatment, a UV cut layer, an organic and/or inorganic oxygen/moisture barrier layer, an easy slip layer, an easy adhesion layer and the like may be applied.
  • surface hydrophilic treatment such as glow discharge treatment, corona discharge treatment or UV ozone treatment on the surface on which the dispersion liquid of the present invention is applied or the surface on which a porous semiconductor fine particle layer described below is formed. ..
  • the photoelectrode substrate constituting the photoelectrode in the present invention is not particularly limited, and (2) base material/present invention, even if (1) base material/conductive film of the present invention is laminated in this order.
  • the conductive film/known conductive film may be laminated in this order, or (3) substrate/known conductive film/conductive film of the invention may be laminated in this order, but the performance is The aspect (3) is preferable because it is stable and easy to manufacture.
  • a substrate for example, PEN
  • a known conductive film for example, ITO
  • a conductive film of the present invention for example, a CNT film
  • porous semiconductor fine particle layer is a porous layer containing semiconductor fine particles. Since it is a porous layer, the amount of the sensitizing dye adsorbed increases, and a dye-sensitized solar cell with high conversion efficiency can be easily obtained.
  • semiconductor fine particles examples include particles of metal oxides such as titanium oxide, zinc oxide, and tin oxide. Titanium oxide is preferred as the semiconductor particles. A layer in which titanium oxide is used as semiconductor fine particles is a titanium oxide layer.
  • the particle size of the semiconductor fine particles is preferably 1 nm or more, usually 500 nm or less, preferably 150 nm or less, and more preferably 80 nm or less.
  • the particles having a particle size of 1 to 100 nm may be used alone or in combination of two or more. Further, particles larger than 100 nm and particles smaller than 500 nm may be further combined.
  • the specific surface area of the porous semiconductor fine particle layer can be increased by using a particle having a particle size of 100 nm or less, and when the particle having a particle size of more than 100 nm is used, the porous semiconductor fine particle layer has a scattering property, and the solar cell The incident light can be efficiently used.
  • the thickness of the porous semiconductor fine particle layer is usually 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more, more preferably 5 ⁇ m or more, preferably 30 ⁇ m or less, and 10 ⁇ m or less. More preferable. Within this range, incident light can be efficiently used in the DSC.
  • the method for forming the porous semiconductor fine particle layer is not particularly limited, and a known method can be appropriately selected and used.
  • the porous semiconductor fine particle layer can be formed by a known method such as a pressing method, a hydrothermal decomposition method, an electrophoretic deposition method, an aerosol deposition method (AD method), a transfer method, and a binder-free coating method.
  • the heating temperature at the time of forming the porous semiconductor fine particle layer is usually 100° C. or higher and 600° C. or lower. When using a plastic or the like for the substrate, it is preferably 200° C. or lower, more preferably 160° C. or lower. preferable.
  • a buffer layer may be formed between the porous semiconductor fine particle layer and the conductive layer of the base material.
  • the composition and manufacturing method of the buffer layer are not particularly limited, for example, metal oxides such as titanium, tin, and niobium are sputter-deposited or CVD-deposited, or an alkoxy compound or chloride of a corresponding metal element is applied to the conductive layer. Formed by that.
  • the thickness of the buffer layer is usually 0.001 nm to 1000 nm, preferably 0.01 nm to 10 nm. Within this range, it is possible to improve the reverse electron reaction of electrons, the adhesion of the porous semiconductor fine particle layer to the conductive layer, the reduction of the series resistance of the module, and the like.
  • the sensitizing dye layer is a layer in which a compound (sensitizing dye) that is excited by light and can transfer electrons to the porous semiconductor fine particle layer is adsorbed on the surface of the porous semiconductor fine particle layer.
  • the sensitizing dye is not particularly limited and can be used by appropriately selecting a sensitizing dye of a known dye-sensitized solar cell, for example, a cyanine dye, a merocyanine dye, an oxonol dye, a xanthene dye, a squarylium dye, Examples thereof include organic dyes such as polymethine dyes, coumarin dyes, riboflavin dyes and perylene dyes; metal complex dyes such as phthalocyanine complexes of metals such as iron, copper and ruthenium and porphyrin complexes; and the like.
  • a sensitizing dye of a known dye-sensitized solar cell for example, a cyanine dye, a merocyanine dye, an oxonol dye, a xanthene dye, a squarylium dye
  • organic dyes such as polymethine dyes, coumarin dyes, riboflavin dyes and perylene
  • N3, N719, N749, D102, D131, D150, N205, HRS-1, MK-2, SK-1 and CYC are typical sensitizing dyes.
  • the organic solvent that dissolves the dye (dye solvent) is preferably degassed, distilled and purified, and dried in advance in order to remove the water and gas existing in the solvent.
  • methanol, ethanol, propanol for example, methanol, ethanol, propanol.
  • Solvents such as alcohols such as; nitriles such as acetonitrile; halogenated hydrocarbons; ethers; amides; esters; carbonic acid esters; ketones; hydrocarbons; aromatics; nitromethane; It may also contain a co-adsorbent such as carboxylic acids having a steroid skeleton such as cholic acid and deoxycholic acid. These dyes, solvents and coadsorbents may be used alone or in combination of two or more.
  • the method for forming the sensitizing dye layer is not particularly limited, and a known method can be appropriately selected and used, for example, a method of immersing the porous semiconductor fine particle layer in a solution of the sensitizing dye, or sensitizing
  • the sensitizing dye layer can be formed by a known method such as a method of applying a dye solution onto the porous semiconductor fine particle layer. After impregnation or coating, it is preferable to wash the substrate containing the porous semiconductor layer and the like with the above-mentioned dye solvent to wash excess dye and the like. After forming the sensitizing dye layer or washing, it may be dried by a known method such as heating, leaving in the air, and drying under reduced pressure.
  • the counter electrode usually has a counter electrode substrate having a conductive film of the present invention formed on a base material, and a catalyst layer formed on the counter electrode substrate.
  • the counter electrode substrate constituting the counter electrode is not particularly limited, and (2) base material/present invention, even if (1) base material/conductive film of the present invention is laminated in this order.
  • the conductive film/known conductive film may be laminated in this order, or (3) substrate/known conductive film/conductive film of the invention may be laminated in this order, but the performance is The aspect (3) is preferable because it is stable and easy to manufacture.
  • the counter electrode substrate having the above configurations (1) to (3) can be used as it is as a counter electrode.
  • the conductive film of the present invention is a CNT film
  • the conductive film exhibits catalytic activity and also serves as a catalyst layer.
  • a counter electrode among others, a substrate (for example, PEN)/a known conductive film (for example, ITO)/a conductive film of the present invention (for example, a CNT film) is used because of its excellent catalytic activity and durability. It is more preferable that the layers are laminated in order.
  • the base material and the known conductive film can be the same as those described in the description of the photoelectrode, and the preferred embodiments are also the same.
  • the catalyst layer functions as a catalyst when electrons are transferred from the counter electrode to the electrolyte layer described later in the organic solar cell.
  • the catalyst layer can be formed of the conductive film (CNT film) of the present invention, but a known catalyst layer can be appropriately selected and used.
  • Examples of the conductive polymer include poly(thiophene-2,5-diyl), poly(3-butylthiophene-2,5-diyl), poly(3-hexylthiophene-2,5-diyl), poly( Polythiophenes such as 2,3-dihydrothieno-[3,4-b]-1,4-dioxin) (PEDOT); polyacetylene and its derivatives; polyaniline and its derivatives; polypyrrole and its derivatives; poly(p-xylenetetrahydrothiophe) Aluminum chloride), poly[(2-methoxy-5-(2'-ethylhexyloxy))-1,4-phenylenevinylene], poly[(2-methoxy-5-(3',7'-dimethyloctyloxy) )-1,4-phenylenevinylene)], poly[2-2′,5′-bis(2′′-ethylhexyloxy)
  • the noble metal particles are not particularly limited as long as they have a catalytic action, and known noble metal particles can be appropriately selected and used. Examples thereof include metal platinum, metal palladium, metal ruthenium, and the like, alone or in alloy, and those having a core-shell structure.
  • the particle diameter of these particles is not particularly limited, but is usually 0.01 nm to 50 nm.
  • the method for forming the catalyst layer is not particularly limited, and a known method can be appropriately selected and used.
  • a conductive polymer, a carbon material, a noble metal particle, or a mixed solution obtained by dissolving or dispersing both a carbon material and a noble metal particle in a suitable solvent is applied or sprayed on a conductive film to obtain a mixture of the mixed solution. This can be done by drying the solvent.
  • the mixed solution may further contain a binder, and as the binder, a hydroxyl group, a carboxyl group, a sulfonyl group, a phosphoric acid, from the viewpoint of the dispersibility of the carbon material and the adhesion to the substrate. It is preferable to use a polymer compound having a functional group such as a group and a sodium salt of these functional groups.
  • the thickness of the catalyst layer is preferably 0.005 ⁇ m or more, and preferably 100 ⁇ m or less.
  • the thickness is more preferably 0.01 ⁇ m to 50 ⁇ m, further preferably 0.1 ⁇ m to 10 ⁇ m, and particularly preferably 0.5 ⁇ m to 5 ⁇ m.
  • the film strength of the catalyst layer, the adhesion, the catalyst performance, the series resistance as a solar cell module, and the like are low, and the performance of the solar cell is excellent.
  • the electrolyte layer is a layer for separating the photoelectrode and the counter electrode and efficiently performing charge transfer.
  • the electrolyte layer is not particularly limited to a solid, liquid, semi-solid such as gel.
  • the electrolyte layer usually contains a supporting electrolyte, a redox couple (a pair of chemical species capable of reversibly converting each other in the form of an oxidant and a reductant in a redox reaction), a solvent and the like.
  • Examples of the supporting electrolyte include (i) salts of alkali metals or alkaline earth metals such as lithium iodide and sodium iodide; (ii) pyridinium salts; compounds having a imidazolium ion quaternary nitrogen atom as a spiro atom; And an ionic liquid containing a cation such as a quaternary ammonium ion.
  • Examples of the redox couple include iodine compound-iodine, bromine compound-bromine, zinc complex, iron complex, cobalt complex and the like.
  • solvent those known as a solvent for forming an electrolyte layer can be used.
  • the solvent include highly polar solvents such as acetonitrile, methoxyacetonitrile, methoxypropionitrile, N,N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate, glycol ether and ⁇ -butyrolactone.
  • an aprotic solvent is preferable.
  • the method for forming the electrolyte layer is not particularly limited, and a known method can be appropriately selected and used. For example, applying a solution (electrolyte solution) containing components of the electrolyte layer under atmospheric pressure or reduced pressure onto the photoelectrode and/or the counter electrode; preparing a cell having the photoelectrode and the counter electrode, and forming a gap between them. It can be formed by injecting an electrolytic solution into.
  • the solar cell of the present invention comprises the above-mentioned electrode of the present invention.
  • the solar cell of the present invention is not particularly limited as long as it has the electrode of the present invention.
  • Examples of the solar cell of the present invention include organic solar cells such as the above-described dye-sensitized solar cell, organic thin film solar cell, and perovskite solar cell. Examples of perovskite solar cells are described in, for example, JP-A-04-049631, JP-A-2015-046583, and JP-A-2016-009737.
  • crystalline silicon solar cells such as single crystal silicon solar cells, polycrystalline silicon solar cells, microcrystalline silicon solar cells, and multi-bond silicon solar cells. Batteries; amorphous silicon solar cells; compound solar cells such as GaAs solar cells, CIS solar cells, CdTe solar cells; and the like.
  • the solar cell of the present invention is not limited to one using the sun as a light source, and may be one using, for example, indoor lighting as a light source. Since the solar cell of the present invention includes the electrode of the present invention, it has high conversion efficiency. Since such characteristics are particularly utilized, the solar cell of the present invention is preferably used as a portable solar cell or an indoor solar cell.
  • the shape of the solar cell is not particularly limited, and there are Z type, W type, parallel type, current collecting array type, monolithic type, and the like.
  • One or more of these solar cells may be combined and connected in series or in parallel, or may be connected in plurality.
  • a connection method known means may be used, and solder, a metal plate, a cable, a flat cable, a flexible base material, a cable, or the like may be appropriately selected.
  • a solar cell or a module may be provided with a take-out electrode for taking an electric current from the module. There is no particular limitation on the position of the extraction electrode, the material, the manufacturing method, etc., and a known method may be used.
  • a metal such as aluminum, nickel, stainless steel, copper, gold, silver or solder, a paste such as carbon, a conductive tape or the like can be used.
  • the extraction electrodes can be appropriately manufactured so that a total of two extraction electrodes are connected to each of the negative electrode and the positive electrode of the solar cell module. Further, the electrodes can be provided with a current collecting wiring for efficiently collecting electrons generated from the cells of the solar battery.
  • the current collecting wiring is not particularly limited, and a known current collecting wiring can be appropriately selected and used.
  • the current collecting wiring is formed by, for example, a sputtering method, a vapor deposition method, a plating method, or a coating method such as an inkjet method or a screen printing method using a conductive paste containing photocurable and/or thermosetting silver or carbon. Can be made.
  • a protective seal for protecting the current collecting wiring from the electrolyte can be used for the current collecting wiring.
  • a thermoplastic resin such as a low-polarity acrylic resin, polyisobutylene, polyisoprene, polybutadiene and an epoxy resin, a heat and/or photocurable resin, or high milan can be used.
  • insulative spacer particles, conductive fine particles, or the like can be used to separate the electrodes of the solar cell module or electrically connect the cells. These may be used by being contained in a sealing resin such as a thermosetting resin for sealing the electrolyte of the solar cell module and/or adhering between the electrodes and/or a thermoplastic resin such as photocurable resin or high milan.
  • a sealing resin such as a thermosetting resin for sealing the electrolyte of the solar cell module and/or adhering between the electrodes and/or a thermoplastic resin such as photocurable resin or high milan.
  • a sealing resin such as a thermosetting resin for sealing the electrolyte of the solar cell module and/or adhering between the electrodes and/or a thermoplastic resin such as photocurable resin or high milan.
  • a sealing resin such as a thermosetting resin for sealing the electrolyte of the solar cell module and/or adhering between the electrodes and/or a thermoplastic resin such as photocurable resin or high
  • the DSC module 100 includes a first substrate 1 and a first substrate 3 including a plurality of (four in the illustrated example) photoelectrodes 2 that are first electrodes and are provided on the first substrate 1 so as to be separated from each other.
  • the second substrate 5 and the second substrate 7 provided with the counter electrodes 6 that are the plurality of (four in the illustrated example) second electrodes provided on the second substrate 5 so as to be separated from each other are the first substrate 3 and the second substrate 7.
  • the partition wall 8 interposed between the second substrate 7 and the second substrate 7, the photoelectrode 2 and the counter electrode 6 forming each cell face each other via the electrolyte layer 4, which is a functional layer (that is, the cell).
  • Each cell of the DSC module 100 includes a photoelectrode 2, a counter electrode 6 facing the photoelectrode 2, and an electrolyte layer 4 provided between the photoelectrode 2 and the counter electrode 6.
  • the DSC module 100 also includes a first extraction electrode 12A connected to the photoelectrode conductive layer 21 forming the photoelectrode 2, and a second extraction electrode 12B connected to the counter electrode conductive layer 61 forming the counter electrode 6. Equipped with.
  • CNT and/or KB paste Dispersibility of dispersion liquid (CNT and/or KB paste)> First, a transparent conductive plastic film (thickness: 186 ⁇ m, surface resistance on conductive layer side: 15 ⁇ ) in which a conductive layer made of indium-tin composite oxide (ITO) is formed on a polyethylene naphthalate (PEN) substrate. / ⁇ ) was prepared. Next, the CNT and/or KB paste (dispersion liquid) obtained in each Example or each Comparative Example was wet jet milled (manufactured) on the surface of the transparent conductive plastic film on which the conductive layer was formed.
  • ITO indium-tin composite oxide
  • PEN polyethylene naphthalate
  • a pseudo-sunlight irradiation device (PEC-L11 type, manufactured by Pexel Technologies, Inc.) in which an AM1.5G filter was mounted on a 150 W xenon lamp light source was used. The light amount was adjusted to 1 sun [AM 1.5G, 100 mW/cm 2 (JIS C8912 class A)].
  • the manufactured solar cell was connected to a source meter (2400 type source meter, manufactured by Keithley), and the following current-voltage characteristics were measured. The output current was measured under the irradiation of light for 1 sun while changing the bias voltage from 0 V to 0.8 V in units of 0.01 V.
  • the output current was measured at each voltage step by changing the voltage and then integrating the values from 0.05 seconds to 0.15 seconds.
  • the bias voltage was also varied in the reverse direction from 0.8 V to 0 V, and the average value of the forward and reverse measurements was used as the photocurrent.
  • the energy conversion efficiency (%) was calculated from the above measurement result of the current-voltage characteristics.
  • the energy conversion efficiency of the solar cell was evaluated according to the following criteria. The evaluation results are shown in Table 1. ⁇ Evaluation criteria>> A: Conversion efficiency is 4.0% or more B: Conversion efficiency is 3.5% or more and less than 4.0% C: Conversion efficiency is 3.0% or more and less than 3.5% D: Conversion efficiency is less than 3.0%
  • Ketjen black manufactured by Lion Specialty Chemicals Co., Ltd., trade name: EC600JD, primary particle size: 34 nm
  • EC600JD primary particle size: 34 nm
  • Dispersant F Phenolsulfonic acid resin (manufactured by Konishi Chemical Industry Co., Ltd.)
  • Dispersant G ⁇ -naphthalenesulfonic acid formalin condensate sodium salt (manufactured by Kao Corporation, trade name: Demol RN)
  • Dispersant H sodium phenolsulfonate (manufactured by Junsei Chemical Co., Ltd.)
  • Dispersant I Norylphenol (Nichika Chemical Co., Ltd.)
  • Example 1 ⁇ Preparation of dispersion> To 500 mL of polyvin, 140 g of pure water and hydrochloric acid were added to adjust the pH to 2.0, and 60 g of ethanol (solvent (C)) was further added to prepare a 200 g solution. To this solution, a 30 mass% alkaline solution of Dispersant A prepared so that the mass ratio (nanocarbon/dispersant) (carbon material (A)/condensate (B)) in Table 1 was added, and SGCNT was further added. In addition, a mixture in a wet state was prepared such that SGCNT was 0.40 mass% and pH was 2.0.
  • the mixture was stirred with a homomixer at 6000 rpm for 30 minutes while cooling the polybin to 25° C. in a water bath to obtain a crude dispersion liquid.
  • the obtained crude dispersion liquid was subjected to 10 Pass treatment at 100 MPa with a wet jet mill (manufacturing company name: Yoshida Machinery Co., Ltd., trade name: Nanoveta) at 100C, and CNT paste as the dispersion liquid.
  • a wet jet mill manufactured company name: Yoshida Machinery Co., Ltd., trade name: Nanoveta
  • a sensitizing dye solution (concentration 0.4 mM) was prepared.
  • An ITO-PEN film (50 mm ⁇ 50 mm 15 ⁇ / ⁇ ) was coated with a isopropyl alcohol solution of titanium isopropoxide having a concentration of 5 mM by a bar coating method, and was heated in an inert oven (Yamato Scientific Co., Ltd.) at 150° C. for 15 minutes. Dried.
  • a thermosetting Ag paste (manufactured by Toyochem Co., Ltd.) was used to print using a screen printing machine (SFA-PC610CTN manufactured by Ceria), and heated in an inert oven (manufactured by Yamato Scientific Co., Ltd.) at 130° C. for 30 minutes.
  • a take-out electrode (thickness 8 ⁇ m) is formed, and a water-based titanium oxide paste (PECC-AW1-01, manufactured by Pexel Technologies Co., Ltd.) is further applied by a screen printing machine, and an inert oven (Yamato Scientific Co., Ltd.) is used. It was dried at 150° C. for 15 minutes to form a porous semiconductor layer (the thickness of the titanium oxide layer was 8 ⁇ m).
  • the substrate on which this porous semiconductor layer was formed was placed in a dye solution (50 cm vat) and immersed at 40° C. for 2 hours. After the immersion, it was washed with an ethanol solution and dried at 40° C. for 24 hours under reduced pressure to prepare a photoelectrode.
  • Sealing agent polybutylene-based photo-curable resin and 8% by mass insulating spacer resin (25 ⁇ m)
  • a vacuum laminating device Width 0.9 mm, height 30 ⁇ m
  • the electrolytic solution was applied to the titanium oxide layer (porous semiconductor fine particle layer) with a dispenser so as to cover one circumference.
  • the counter electrode was placed in a vacuum bonding apparatus, superposed in a vacuum, and UV irradiation was performed with a metal halide lamp at an integrated light amount of 3000 mJ/cm 2 to cure the sealing material and bonding was performed.
  • the vacuum was released to atmospheric pressure and the organic solar cell was taken out.
  • Example 1 instead of preparing the dispersion liquid (CNT paste) under the conditions shown in Example 1 of Table 1, dispersion was carried out under the conditions shown in Examples 2 to 9 and Comparative Examples 1 to 4 of Table 1.
  • the preparation of the dispersion liquid, the preparation of the dye solution, the preparation of the photoelectrode, the preparation of the counter electrode, the preparation of the organic solar cell, and Various evaluations were performed. The results are shown in Table 1.
  • ion-exchanged water pH 7.0
  • Example 2> In the same manner as in Example 1 except that a neutral rinse solution was used instead of the alkaline rinse solution in Example 1, preparation of a dispersion, preparation of a dye solution, preparation of a photoelectrode, counter electrode. Was manufactured, an organic solar cell was manufactured, and various evaluations were performed. The results are shown in Table 1.
  • Example 3> In the same manner as in Example 2 except that single-walled carbon nanotubes (HiPco) were used instead of single-walled carbon nanotubes (SGCNT) in Example 2, preparation of a dispersion liquid, preparation of a dye solution, and photoelectrode Was manufactured, a counter electrode was manufactured, an organic solar cell was manufactured, and various evaluations were performed. The results are shown in Table 1.
  • HiPco single-walled carbon nanotubes
  • SGCNT single-walled carbon nanotubes
  • Example 4> In the same manner as in Example 2 except that 4.00% by mass of Ketjen Black (KB) was used in place of 0.40% by mass of the single-walled carbon nanotube (SGCNT) in Example 2, Preparation, preparation of dye solution, preparation of photoelectrode, preparation of counter electrode, preparation of organic solar cell, and various evaluations were performed. The results are shown in Table 1.
  • Example 5> In Example 1, instead of using single-walled carbon nanotubes (SGCNT), a mixture of single-walled carbon nanotubes (SGCNT) and Ketjenblack (KB) (blending ratio (mass %): 80/20) was used.
  • Example 6 In the same manner as in Example 2 except that the dispersant B was used instead of the dispersant A in Example 2, preparation of the dispersion liquid, preparation of the dye solution, preparation of the photoelectrode, preparation of the counter electrode, Fabrication of an organic solar cell and various evaluations were performed. The results are shown in Table 1.
  • Example 7> In the same manner as in Example 2 except that the dispersant C was used instead of the dispersant A in Example 2, preparation of the dispersion liquid, preparation of the dye solution, preparation of the photoelectrode, preparation of the counter electrode, Fabrication of an organic solar cell and various evaluations were performed. The results are shown in Table 1.
  • Example 8> In the same manner as in Example 2 except that the dispersant D was used instead of the dispersant A in Example 2, preparation of the dispersion liquid, preparation of the dye solution, preparation of the photoelectrode, preparation of the counter electrode, Fabrication of an organic solar cell and various evaluations were performed. The results are shown in Table 1.
  • Example 9> In the same manner as in Example 2 except that the dispersant E was used instead of the dispersant A in Example 2, preparation of a dispersion liquid, preparation of a dye solution, preparation of a photoelectrode, preparation of a counter electrode, Fabrication of an organic solar cell and various evaluations were performed. The results are shown in Table 1.
  • ⁇ Comparative Example 1> A dispersion liquid was prepared in the same manner as in Example 2 except that the dispersant A was used in an amount of 20 times the mass of the carbon material instead of the dispersant A used in the amount of 2.5 times the mass of the carbon material. It was The results are shown in Table 1. Since the dispersibility was poor, a coating film could not be obtained by screen printing, and other evaluations were not conducted.
  • ⁇ Comparative example 2> Preparation of dispersion liquid and dye in the same manner as in Example 2 except that the dispersant A was used in an amount of 20 times by mass of the carbon material instead of the dispersing material A in an amount of 2.5 times by mass of the carbon material.
  • ⁇ Comparative example 3> Preparation of dispersion liquid and dye in the same manner as in Example 2 except that the dispersant A was used 20 times by mass of the carbon material instead of the dispersant A 2.5 times by mass of the carbon material.
  • a dispersion liquid capable of improving the coating property (wettability) with respect to a substrate and forming a conductive film having high adhesion to the substrate.
  • a conductive film having high adhesion to a base material a method for producing the conductive film, an electrode having the conductive film and having high conductivity, and a solar cell having the electrode and having high conversion efficiency. Can be provided.

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