WO2010061901A1 - 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 - Google Patents

光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 Download PDF

Info

Publication number
WO2010061901A1
WO2010061901A1 PCT/JP2009/069981 JP2009069981W WO2010061901A1 WO 2010061901 A1 WO2010061901 A1 WO 2010061901A1 JP 2009069981 W JP2009069981 W JP 2009069981W WO 2010061901 A1 WO2010061901 A1 WO 2010061901A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon material
photoelectric conversion
electrolyte
conversion element
ionic liquid
Prior art date
Application number
PCT/JP2009/069981
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
善正 今▲崎▼
司 丸山
Original Assignee
横浜ゴム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to JP2010513520A priority Critical patent/JP4557097B2/ja
Priority to US13/131,674 priority patent/US8338692B2/en
Priority to CN200980147543.3A priority patent/CN102227847B/zh
Priority to DE112009003578.7T priority patent/DE112009003578B4/de
Publication of WO2010061901A1 publication Critical patent/WO2010061901A1/ja

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to an electrolyte for a photoelectric conversion element, a photoelectric conversion element using the electrolyte, and a dye-sensitized solar cell.
  • dye-sensitized solar cells developed by Grezel, etc. of Switzerland have high photoelectric conversion efficiency among solar cells using organic materials, and are less expensive to manufacture than silicon-based solar cells. It is also attracting attention as a new type of solar cell due to its advantages such as low price.
  • dye-sensitized solar cells are electrochemical cells, organic electrolytes or ionic liquids are used as electrolytes. When organic electrolytes are used, they may volatilize or be depleted during long-term use. However, when using ionic liquids, volatilization and depletion during long-term use can be prevented, but there are durability problems such as structural deterioration due to liquid leakage. It was. In view of this, studies have been made to change the electrolyte from liquid to gel or solid for the purpose of preventing volatilization and leakage of the electrolyte and ensuring long-term stability and durability of the solar cell.
  • Patent Document 1 describes “a gel-like electrolyte composition containing an ionic liquid and conductive particles as main components” ([Claim 1] and [Claim 2]).
  • Patent Document 2 discloses that “a dye-sensitized photoelectric conversion element having a porous photoelectrode layer made of dye-sensitized semiconductor particles, a charge transport layer, and a counter electrode layer in this order, The layer is made of a solid mixture containing 1 to 50% by mass of a p-type conductive polymer, 5 to 50% by mass of a carbon material, and 20 to 85% by mass of an ionic liquid. Conversion element ”is described ([Claim 1]).
  • the present inventor has revealed that the energy conversion efficiency is not sufficient. This is because when a mixture of a p-type conductive polymer (for example, polyaniline, polypyrrole, etc.), a carbon material (for example, acetylene black, etc.) and an ionic liquid is used as the charge transport layer, the carbon material (especially acetylene black) It is considered that the ability to retain the ionic liquid itself (retention ability) is low and the retention ability is further lowered by mixing with the p-type conductive polymer.
  • a p-type conductive polymer for example, polyaniline, polypyrrole, etc.
  • a carbon material for example, acetylene black, etc.
  • an ionic liquid the charge transport layer
  • the carbon material especially acetylene black
  • the present invention provides an electrolyte for a photoelectric conversion element that can achieve high energy conversion efficiency even when substantially not containing iodine, and a photoelectric conversion element and a dye-sensitized solar cell using the electrolyte. Objective.
  • the present invention provides the following (a) to (o).
  • R 1 represents a hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms, and has a substituent that may contain a heteroatom having 1 to 20 carbon atoms. May be.
  • R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. However, when the nitrogen atom contains a double bond, R 3 does not exist.
  • Q represents a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom
  • R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms. Represents a group and may contain a heteroatom. However, when Q is an oxygen atom or a sulfur atom, R 7 does not exist.
  • the carbon material (C) other than the carbon material (B) the carbon material (C) containing a carbon material having a pH of 2 to 6 measured by a pH measuring method defined in JIS Z8802
  • the electrolyte for photoelectric conversion elements as described.
  • the total content of the carbon material (B) and the other carbon material (C) is 10 to 50 parts by mass with respect to 100 parts by mass of the ionic liquid (A).
  • the electrolyte for photoelectric conversion elements in any one of.
  • the content ratio [carbon material (B) / other carbon material (C)] of the carbon material (B) and the other carbon material (C) is 99.9 / 0.1 to 60
  • (N) a photoelectrode having a transparent conductive film and a metal oxide semiconductor porous film; A counter electrode disposed to face the photoelectrode; An electrolyte layer disposed between the photoelectrode and the counter electrode; A photoelectric conversion element wherein the electrolyte layer is the electrolyte for a photoelectric conversion element according to any one of (a) to (m).
  • an electrolyte for a photoelectric conversion element that can achieve high energy conversion efficiency without substantially containing iodine, and a photoelectric conversion element and dye sensitization using the electrolyte This is useful because a solar cell can be provided.
  • the electrolyte for photoelectric conversion elements of the present invention is very useful because it can achieve high energy conversion efficiency without using a p-type conductive polymer such as polyaniline.
  • FIG. 1 is a schematic cross-sectional view showing an example of the basic configuration of the photoelectric conversion element of the present invention.
  • FIG. 2 is a drawing showing the basic configuration of the solar cell of the present invention used in Examples and the like.
  • the electrolyte for photoelectric conversion elements of the present invention (hereinafter also simply referred to as “the electrolyte of the present invention”) contains an ionic liquid (A) and a carbon material (B) having a specific surface area of 1000 to 3500 m 2 / g.
  • the content of the carbon material (B) is 10 to 50 parts by mass with respect to 100 parts by mass of the ionic liquid (A).
  • the ionic liquid (A) used for the electrolyte of the present invention is not particularly limited, and any ionic liquid used as a conventional electrolyte can be used.
  • any ionic liquid used as a conventional electrolyte can be used.
  • Secondary ammonium salts, imidazolium salts, pyridinium salts, pyrrolidinium salts, piperidinium salts, and the like can be used.
  • the ionic liquid (A) has a cation and an anion which is a counter ion.
  • a cation the cation represented by following formula (1) or (2) is illustrated suitably.
  • R 1 represents a hydrocarbon group that may contain a heteroatom having 1 to 20 carbon atoms, and has a substituent that may contain a heteroatom having 1 to 20 carbon atoms. May be.
  • R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. However, when the nitrogen atom contains a double bond, R 3 does not exist.
  • Q represents a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom
  • R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms. Represents a group and may contain a heteroatom. However, when Q is an oxygen atom or a sulfur atom, R 7 does not exist.
  • the hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms of R 1 in the above formula (1) includes a ring structure together with a nitrogen atom (ammonium ion) in the above formula (1). It is preferable to take it.
  • the substituent which may contain a hetero atom having 1 to 20 carbon atoms which R 1 in the above formula (1) may have is an alkyl group having 1 to 12 carbon atoms (for example, methyl Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.), alkoxy group having 1 to 12 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group) Group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, n-hexoxy group, 1,2-dimethylbutoxy group, etc.), alkyl alkoxy group having 2 to 12 carbon atoms (for example, methylene methoxy (-CH 2 OCH 3), ethylene methoxy (-CH 2 CH 2 OCH 3) , n- propylene - iso -
  • an alkyl group having 1 to 12 carbon atoms for example, Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
  • alkoxy group having 1 to 12 carbon atoms for example, methoxy group, ethoxy group, n-propoxy group, iso -Propoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, n-hexoxy group, 1,2-dimethylbutoxy group, etc.
  • alkyl alkoxy group having 2 to 12 carbon atoms for example, , Methylene methoxy group (—CH 2 OCH 3 ), ethylene methoxy group (—CH 2 CH 2 OCH 3 ),
  • the hydrocarbon group which may contain a hetero atom having 1 to 8 carbon atoms of R 4 , R 5 , R 6 and R 7 is specifically 1 to 1 carbon atom.
  • 8 alkyl groups for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
  • alkoxy groups having 1 to 8 carbon atoms for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, n-hexoxy group, 1,2-dimethylbutoxy group, etc.
  • C 2-8 Alkyl alkoxy groups for example, methylene methoxy group (—CH 2 OCH 3 ), ethylene methoxy group (—CH 2 CH 2 OCH 3 ), n-propylene-is
  • Examples of the cation represented by the above formula (1) include imidazolium ion, pyridinium ion, pyrrolidinium ion, piperidinium ion, and the like.
  • a cation represented by any of the following formulas (3) to (6) is preferably exemplified.
  • the cation represented by the following formulas (3) and (5) is the photoelectric conversion of the photoelectric conversion element using the electrolyte of the present invention (hereinafter also referred to as “the photoelectric conversion element of the present invention”). This is preferable because the efficiency tends to be better.
  • R 8 to R 40 each independently represents a hydrocarbon group that may contain a nitrogen atom having 1 to 20 carbon atoms. More specifically, the following cations are mentioned.
  • Examples of the cation represented by the above formula (2) include organic cations such as ammonium ion, sulfonium ion, and phosphonium ion. Specifically, the following cations are preferably exemplified. Among these, aliphatic quaternary ammonium ions are preferable because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention tends to be better.
  • anions of the ionic liquid (A) include I ⁇ , Br ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ and CH 3.
  • bromine ions (Br ⁇ ) and iodine ions (I ⁇ ) are preferable because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention tends to be better, and iodine ions (I ⁇ ). More preferably.
  • an ionic liquid (A) what consists of a combination of the cation and the anion illustrated above, etc. are mentioned, for example.
  • an ionic liquid having imidazolium ions as cations and iodine ions as anions is preferable.
  • the method for synthesizing the ionic liquid (A) is not particularly limited, and various ionic liquids composed of combinations of cations and anions exemplified above can be synthesized by a conventionally known method.
  • Examples of such an ionic liquid (A) include 1-methyl-3-methylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1-methyl-3-pentylimidazolium iodide, 1-methyl-3-methylimidazolium iodide, 1-methyl-3-pentylimidazolium iodide, In addition to synthetic products such as hexyl-3-methylimidazolium iodide, 1-((2-methoxyethoxy) ethyl) -3-((2-methoxyethoxy) ethyl) imidazolium iodide, use commercially available products Specifically, for example, 1-methyl-3-propylimidazolium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-methyl-3-butylimidazolium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-methyl-
  • the content of the ionic liquid (A) is preferably 50 to 95% by mass and more preferably 65 to 95% by mass with respect to the total mass of the electrolyte of the present invention.
  • the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
  • the carbon material (B) used for the electrolyte of the present invention is a carbon material having a specific surface area of 1000 to 3500 m 2 / g.
  • the specific surface area refers to a measured value measured using the BET method by nitrogen adsorption according to the method defined in JIS K1477.
  • a high energy conversion efficiency can be achieved without substantially containing iodine. can do.
  • a carbon material (B) having a surface area larger than that of carbon black (acetylene black) or graphite is used to form an electrolyte in which the carbon material (B) sufficiently holds the ionic liquid (A). It is considered that this is because the ionic liquid (A) can be sufficiently filled in the metal oxide semiconductor porous film described later.
  • the carbon material (B) having a large surface area has a function like a sponge capable of taking in and out the ionic liquid (A), each interface, that is, an interface between the electrolyte and a metal oxide semiconductor porous film described later, This is considered to be because the formation of a layer (ionic liquid layer) in which the ionic liquid (A) formed at the interface between the carbon particles and the interface between the electrolyte and the counter electrode is localized is suppressed. If the ionic liquid (A) is not present in the electrolyte, it does not function as an electrolyte for the photoelectric conversion element. For example, in the dye-sensitized photoelectric conversion element described in Patent Document 2, the ionic liquid is the above-described one.
  • the content of the carbon material (B) is 100 masses of the ionic liquid (A).
  • the amount is preferably 15 to 45 parts by mass, more preferably 25 to 40 parts by mass with respect to parts.
  • the specific surface area of the carbon material (B) is preferably 1100 to 3200 m 2 / g, and more preferably 1200 to 2800 m 2 / g.
  • the specific surface area is within this range, the filling of the metal oxide semiconductor porous film with the ionic liquid (A) and the function of the sponge described above work effectively, and the photoelectric conversion efficiency of the photoelectric conversion element of the present invention is better. It becomes.
  • the primary average particle diameter of the carbon material (B) is preferably 0.5 to 120 ⁇ m, more preferably 0.8 to 80 ⁇ m.
  • the primary average particle diameter is a value measured by a method of measuring the primary average particle diameter of a normal carbon material (for example, activated carbon or the like).
  • the carbon material (B) is It means a 50% volume cumulative diameter (D50) measured by using a laser diffraction particle size distribution analyzer (for example, SALD2000J (registered trademark, manufactured by Shimadzu Corporation)) after being dispersed in a neutral detergent-containing aqueous solution.
  • the specific resistance of the carbon material (B) is preferably 1 ⁇ 10 ⁇ 4 to 5 ⁇ 10 2 ⁇ ⁇ cm, and preferably 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 2 ⁇ ⁇ cm. Is more preferable, and 5 ⁇ 10 ⁇ 2 to 50 ⁇ ⁇ cm is more preferable.
  • the specific resistance means a value obtained by measuring specific resistance (volume specific resistance value) by a two-terminal measurement method using a low resistivity meter.
  • the specific resistance of acetylene black, which will be described later, is 3 ⁇ 10 ⁇ 2 ⁇ ⁇ cm.
  • a carbon material (B) specifically, for example, activated carbon (specific surface area: 1000 to 2800 m 2 / g, primary average particle size: 0.5 to 120 ⁇ m, specific resistance: 1.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm), boron-containing porous carbon material (specific surface area: 1000 to 2000 m 2 / g, primary average particle size: 0.5 to 100 ⁇ m, specific resistance: 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm), nitrogen Containing porous carbon materials (specific surface area: 1000 to 2000 m 2 / g, primary average particle size: 0.5 to 100 ⁇ m, specific resistance: 1 ⁇ 10 ⁇ 1 ⁇ cm), etc. Or two or more of them may be used in combination.
  • activated carbon specifically surface area: 1000 to 2800 m 2 / g, primary average particle size: 0.5 to 120 ⁇ m, specific resistance: 1.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm
  • boron-containing porous carbon material specifically surface area: 1000 to 2000 m 2
  • activated carbon is preferable because it is easily available.
  • the activated carbon is not particularly limited, and activated carbon particles used in known carbon electrodes and the like can be used. Specific examples thereof include coconut shell, wood powder, petroleum pitch, phenol resin, etc., water vapor, various chemicals, alkali Activated carbon particles activated using the above, etc., and these may be used alone or in combination of two or more.
  • the electrolyte of the present invention includes other carbon materials (C) such as acetylene black (C1), boron-modified acetylene black (C2), and JIS Z8802.
  • C1 acetylene black
  • C2 boron-modified acetylene black
  • JIS Z8802. One or more selected from the group consisting of a carbon material (C3) having a pH of 2 to 6 measured by the pH measurement method and carbon black (C4) having a nitrogen adsorption specific surface area of 90 m 2 / g or more. Can be used.
  • Two or more of these carbon materials (C) can be used in combination, but it is preferable to use a boron-modified acetylene black (C2) and a carbon material (C3) described later in combination.
  • the acetylene black (C1) that can be used in the electrolyte of the present invention is not particularly limited, and is a carbon black having high crystallinity obtained by thermal decomposition of acetylene gas, and is a conventionally known one used as a conductivity imparting agent. Can be used.
  • acetylene black (C1) specifically, for example, acetylene black (denka black powder, specific surface area: 68 m 2 / g, primary average particle size: 400 nm, specific resistance: 3 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, manufactured by Denki Kagaku Kogyo Co., Ltd.).
  • the boron-modified acetylene black (C2) that can be used in the electrolyte of the present invention is not particularly limited, and specific examples thereof include boron-modified acetylene black (Denka Black BMAB, specific surface area: 50 m 2 / g, primary average particle diameter). : 35 nm, specific resistance: 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, manufactured by Denki Kagaku Kogyo Co., Ltd.) and the like.
  • the photoelectric conversion efficiency of the photoelectric conversion element of the present invention is better when the boron-modified acetylene black is used than when the acetylene black (C1) is used.
  • the carbon material (C3) that can be used for the electrolyte of the present invention is a carbon material having a pH of 2 to 6 measured by the pH measurement method defined in JIS Z8802. Specifically, the pH is measured as follows. First, 5 g of a carbon material sample is weighed into a beaker, 50 mL of water is added thereto, and heated until the water boils. Next, the heated dispersion is cooled to room temperature, and after the carbon material is allowed to settle, the supernatant is removed, leaving a mud. An electrode of a glass electrode pH meter is placed in this mud and measured by the pH measurement method specified in JIS Z8802-1984.
  • the primary average particle diameter of the carbon material (C3) is preferably 0.010 to 0.050 ⁇ m, and more preferably 0.010 to 0.035 ⁇ m.
  • the primary average particle diameter is a value measured by a method of measuring a primary average particle diameter of a normal carbon material (for example, furnace carbon black or the like). It means the arithmetic mean diameter obtained by observation with an electron microscope.
  • Examples of such a carbon material (C3) include acidic carbon black to which acidic groups such as phenolic hydroxyl group, carboxy group, quinone group, and lactone group are attached or bonded; pigment carbon black; color carbon black; These may be used alone or in combination of two or more.
  • acidic carbon black is preferable because it can be easily mixed with the ionic liquid (A) described above and the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
  • the carbon black for attaching the hydroxyl group and the like used for the acidic carbon black is not particularly limited, and carbon blacks that are usually used such as oil furnace black, gas furnace black, thermal black, channel black (gas black), etc. Can be used.
  • Examples of the method for attaching a hydroxyl group and the like include a usual ozone treatment, plasma treatment, liquid phase oxidation treatment, and the like, and a method disclosed in JP-A-2004-238111.
  • acidic carbon black although channel black (gas black) itself which has many acidic groups (phenolic hydroxyl group, carboxy group, etc. which were illustrated above) on the carbon black surface can also be used, a commercial item is used. Specifically, for example, # 2200B manufactured by Mitsubishi Chemical Corporation (pH: 3.5, primary average particle size: 0.018 ⁇ m), # 1000 (pH: 3.5, primary average particle size) : 0.018 ⁇ m), # 970 (pH: 3.5, primary average particle size: 0.016 ⁇ m), MA77 (pH: 2.5, primary average particle size: 0.023 ⁇ m), MA7 (pH: 3) Primary average particle size: 0.024 ⁇ m), MA8 (pH: 3, primary average particle size: 0.024 ⁇ m), MA11 (pH: 3.5, primary average particle size: 0.029 ⁇ m), MA10 (PH: 3.5, primary average particle size: 0.024 ⁇ m), MA100R (pH: 3.5, primary average particle size: 3.5, primary average particle
  • Special Black 6 (pH: 2.5, primary average particle size: 17 nm), Special Black 5 (pH: 3.0, primary average particle size: 20 nm), Special Black 4 (pH: 3.0, manufactured by Degussa Evonik) Primary average particle size: 25 nm), Special Black 4A (pH: 3.0, primary average particle size: 25 nm), Special Black 550 (pH: 2.8, primary average particle size: 25 nm), SpecialpH Black 100 (pH: 3.3, primary average particle size: 50 nm), Special Black 250 (pH: 3.1, primary average particle size: 56 nm), Special Black 350 (pH: 3.5, primary average particle size: 31 nm), Printex 150T (PH: 4.0, primary average particle size: 29 nm), Color Black FW1 (pH: 3.5, primary average particle size: 13 nm), Color Black FW18 (pH: 4.5, primary average particle size) : 15nm), Color Black FW285 (pH: 3.5, primary average
  • Toka Black # 8300F (pH: 5.0, primary average particle size: 16 nm) and Toka Black # 8500F (pH: 5.5, primary average particle size: 14 nm) manufactured by Tokai Carbon Co., Ltd .; Can do.
  • the pH is 3 to 5.5 from the viewpoint of increasing the temporal stability of the electrolyte for photoelectric conversion elements of the present invention and further improving the photoelectric conversion efficiency of the photoelectric conversion elements of the present invention. preferable.
  • the carbon black (C4) that can be used for the electrolyte of the present invention is not particularly limited as long as the nitrogen adsorption specific surface area is 90 m 2 / g or more.
  • the nitrogen adsorption specific surface area is a surrogate property of the surface area that carbon black can be used for adsorption with rubber molecules, and the nitrogen adsorption amount on the surface of carbon black is defined as JIS K6217-7: 2008 “Part 7: Rubber compound. -Values measured in accordance with "How to obtain the multipoint nitrogen specific surface area and statistical thickness specific surface area".
  • the nitrogen adsorption specific surface area is preferred to use carbon black 90 ⁇ 200m 2 / g, 100 ⁇ 180m 2 / It is more preferable to use g carbon black.
  • the carbon black (C4) is preferably carbon black having a pH of 7 to 13 measured by the pH measuring method defined in JIS Z8802, more preferably a carbon black having a pH of 7 to 11. It is.
  • the measurement of the pH is specifically performed as follows in the same manner as described in the carbon material (C3). First, 5 g of a carbon black sample is weighed in a beaker, 50 mL of water is added thereto, and heated until the water boils. Next, the heated dispersion is cooled to room temperature, carbon black is allowed to settle, and then the supernatant is removed, leaving a mud. An electrode of a glass electrode pH meter is placed in this mud and measured by the pH measurement method specified in JIS Z8802-1984.
  • a commercial item can be used as such carbon black (C4).
  • C4 carbon black
  • SAF nitrogen adsorption specific surface area: 151m 2 /g,pH:7.3, manufactured by Cabot Japan K.K.
  • ISAF nitrogen adsorption specific surface area: 117m 2 / g, pH: 7 .5, manufactured by Cabot Japan K.K.
  • ISAF nitrogen adsorption specific surface area: 119m 2 /g,pH:7.5, manufactured by Cabot Japan K.K.
  • ISAF N219, nitrogen adsorption specific surface area: 106m 2 / g, pH : 7.5, manufactured by Tokai Carbon Co., Ltd.
  • HAF nitrogen adsorption specific surface area: 93 m 2 / g, pH: 7.5, manufactured by Tokai Carbon Co., Ltd.
  • HAF nitrogen adsorption specific surface area: 93 m 2 / g, pH: 7.5, manufactured by Tokai Carbon Co., Ltd.
  • the primary average particle diameter of the carbon black (C4) is preferably 5 to 30 nm, and more preferably 5 to 25 nm.
  • the primary average particle diameter means the arithmetic average diameter obtained by observing the carbon black particles with an electron microscope, as described in the carbon material (C3).
  • the other carbon material (C) when the other carbon material (C) is contained, 100 masses of the ionic liquid (A) can be achieved because higher energy conversion efficiency can be achieved without substantially containing iodine.
  • the total amount of the carbon material (B) and the other carbon material (C) is preferably 10 to 50 parts by mass with respect to parts.
  • the ratio [carbon material (B) / other carbon material (C)] of the carbon material (B) and the other carbon material (C) is 99.9 / 0.1. It is preferably ⁇ 60 / 40.
  • any two or more of acetylene black (C1), boron-modified acetylene black (C2), carbon material (C3), and carbon black (C4) were used as the other carbon material (C).
  • C1 acetylene black
  • C2 boron-modified acetylene black
  • C3 carbon material
  • C4 carbon black
  • the carbon material (C3) is an anion derived from an acidic group (such as the phenolic hydroxyl group or carboxy group exemplified above) present as a functional group on the surface of the carbon material.
  • an acidic group such as the phenolic hydroxyl group or carboxy group exemplified above
  • carboxylate, phenolate, etc. interact with the cation of the ionic liquid (A) described above.
  • the presence of functional groups on the surface of the carbon material makes it more hydrophilic than general carbon black and graphite, and it is also considered that the dispersion in the ionic liquid (A) described above is easy. .
  • carbon black (C4) having a large nitrogen specific surface area is similar to the above-described carbon material (B), and the sponge ionic liquid (A) can be taken in and out.
  • the ionic liquid (A) formed at each interface that is, the interface between the electrolyte and the metal oxide semiconductor porous film described later, the interface between the carbon particles, and the interface between the electrolyte and the counter electrode.
  • carbon black (C4) has a well-developed structure, so that the electron conductivity is improved. From these results, the photoelectric conversion element This is probably because the open-circuit voltage has increased.
  • the open circuit voltage is the voltage between the terminals when no current is flowing through the power supply terminal. Light is emitted when the reverse voltage (bias voltage) is applied to the electrodes and the bias voltage is gradually increased. The voltage generated when the generated current stops flowing against this bias voltage (when the current value is zero).
  • the carbon material (B) and the other carbon are added from the viewpoint of filling the metal oxide semiconductor porous film with the ionic liquid (A) and enhancing the function and charge transfer of the sponge.
  • the total content of the material (C) is more preferably 15 to 45 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the ionic liquid (A).
  • the ratio of the content of the carbon material (B) and the other carbon material (C) [carbon material (B) / other carbon material (C)] is 99/1 to 65. / 35 is more preferable, and 98/2 to 70/30 is still more preferable.
  • the electrolyte of the present invention can contain silicon oxide and / or metal oxide because the photoelectric conversion efficiency of the photoelectric conversion element of the present invention is further improved. This is considered to be because the arrangement of cations (for example, imidazolium ions) contained in the ionic liquid (A) described above is improved and the movement of electrons proceeds smoothly.
  • cations for example, imidazolium ions
  • silicon oxide that can be used in the electrolyte of the present invention is not particularly limited, and conventionally known ones can be used. Specific examples of silicon oxide include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, colloidal silica, and the like.
  • silicon oxide commercially available products can be used, and specifically, for example, Z1165MP (manufactured by Rodia), AEROSIL200 (manufactured by Deguss), AEROSIL300 (manufactured by Deguss) and the like can be used. it can.
  • the metal oxide that can be used in the electrolyte of the present invention is not particularly limited, and conventionally known metal oxides can be used.
  • the metal oxide include titanium oxide (titanium dioxide), tin oxide, zinc oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, vanadium oxide, niobium oxide, and the like. May be used alone or in combination of two or more.
  • titanium oxide, zinc oxide, niobium oxide, tungsten oxide, and zirconium oxide are preferable from the viewpoint of high photoelectric conversion capability.
  • the total content of the silicon oxide and / or metal oxide and the carbon material (B) and the other carbon material (C) optionally contained is the ionic liquid (A).
  • the amount is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass.
  • the carbon material (B), and the other carbon material (C) optionally contained is within this range, iodine is substantially not included. Even higher energy conversion efficiency can be achieved.
  • the silicon oxide and / or metal oxide hereinafter referred to as “silicon oxide or the like” in this paragraph
  • the carbon material (B) the carbon material optionally contained ( C)
  • the content ratio is preferably 1/99 to 50/50. More preferably, it is ⁇ 40 / 60.
  • the electrolyte of the present invention can be added with a redox pair (redox pair).
  • redox pair any one generally used or usable in a dye-sensitized solar cell can be used as long as the object of the present invention is not impaired.
  • metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium salts; sulfur compounds of disulfide compounds and mercapto compounds; hydroquinones; quinones; etc., and these may be used alone. Two or more kinds may be used in combination.
  • the electrolyte of this invention can add inorganic salt and / or organic salt from a viewpoint of improving the short circuit current of the photoelectric conversion element of this invention.
  • inorganic salts and organic salts include alkali metal, alkaline earth metal salts, and the like.
  • lithium iodide sodium iodide, potassium iodide, magnesium iodide, calcium iodide
  • examples include lithium trifluoroacetate, sodium trifluoroacetate, lithium thiocyanate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, and lithium bis (trifluoromethanesulfonyl) imide. These may be used alone or in combination of two or more.
  • the amount of the inorganic salt or organic salt added is not particularly limited, and can be the same as before as long as the object of the present invention is not impaired.
  • the electrolyte of this invention can add pyridines and benzimidazoles from a viewpoint of improving the open circuit voltage of the photoelectric conversion element of this invention.
  • alkyl pyridines such as methyl pyridine, ethyl pyridine, propyl pyridine and butyl pyridine
  • alkyl imidazoles such as methyl imidazole, ethyl imidazole and propyl imidazole
  • alkyl such as methyl benzimidazole, ethyl benzimidazole and propyl benzimidazole Benzimidazoles; and the like.
  • alkyl pyridines such as methyl pyridine, ethyl pyridine, propyl pyridine and butyl pyridine
  • alkyl imidazoles such as methyl imidazole, ethyl imidazole and propyl imidazole
  • alkyl such as methyl benzimidazole,
  • An organic solvent may be added to the electrolyte of the present invention.
  • Specific examples thereof include carbonates such as ethylene carbonate and propylene carbonate; ethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; ethylene glycol monoalkyl.
  • Alcohols such as ether and propylene glycol monoalkyl ether; Polyhydric alcohols such as ethylene glycol and propylene glycol; Nitriles such as propionitrile, methoxypropionitrile and cyanoethyl ether; Amides such as dimethylformamide and N-methylpyrrolidone Aprotic polar solvents such as dimethyl sulfoxide, sulfolane, etc., and these may be used alone or in combination of two or more.
  • the content of the organic solvent is not particularly limited, and can be conventional as long as the object of the present invention is not impaired.
  • the method for producing the electrolyte of the present invention is not particularly limited.
  • the ionic liquid (A) and the carbon material (B) described above, and other carbon materials (C), silicon oxide, metal oxides, and the like that are optionally contained. Mix well, using a ball mill, sand mill, pigment disperser, pulverizer, ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, roll, kneader, etc. at room temperature or under heating (eg 40-150 ° C.) It can be produced by mixing and uniformly dispersing (kneading).
  • an organic solvent for example, , Toluene, etc.
  • the organic solvent may be distilled off under vacuum.
  • the ionic liquid (A) and the carbon material (B) described above and other carbon materials (C), silicon oxide, metal oxides and the like that are optionally contained are mixed, the ionic liquid (A) is converted into the carbon.
  • the carbon material (B) that has been finely pulverized by a known pulverizer such as a ball mill or a jet mill may be used.
  • a known pulverizer such as a ball mill or a jet mill
  • the above-described ionic liquid (A) and carbon material (B) may be optionally contained in a mixture of other carbon material (C), silicon oxide, metal oxide or the like at room temperature or under heating.
  • the pressure reduction treatment may be performed at (for example, 40 to 150 ° C.).
  • the electrolyte of the present invention contains the above-mentioned other carbon material (C)
  • the above-described ionic liquid (A) and other carbon material (C) are mixed to form a dispersion (
  • the photoelectric conversion efficiency of the photoelectric conversion element of this invention becomes more favorable. This is because the other carbon material (C) is unevenly distributed in the ionic liquid (A), and the ionic liquid (A) that cannot be held by the carbon material (B) is acetylene black (C1) or boron-modified. It is considered that it contributes to the promotion of charge transfer together with acetylene black (C2), and the carbon material (C3) interacts with the cation of the ionic liquid (A) described above.
  • FIG. 1 is a schematic cross-sectional view showing an example of the basic configuration of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element of the present invention includes a photoelectrode having a transparent conductive film and a metal oxide semiconductor porous film, a counter electrode disposed to face the photoelectrode, and the photoelectrode and the counter electrode. It is a photoelectric conversion element which has the made electrolyte layer.
  • the photoelectrode includes a transparent substrate 1, a transparent conductive film 2, and an oxide semiconductor porous film 3.
  • the transparent substrate 1 preferably has good light transmittance.
  • Specific examples thereof include a glass substrate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyphenylene sulfide, and cyclic olefin polymer.
  • resin substrates (films) such as polyethersulfone, polysulfone, polyetherimide, polyarylate, triacetylcellulose, and polymethylmethacrylate.
  • the transparent conductive film 2 specifically, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine, zinc oxide doped with aluminum or gallium, indium oxide doped with tin, etc. Is mentioned.
  • the thickness of the transparent conductive film 2 is preferably about 0.01 to 1.0 ⁇ m.
  • the method for providing the transparent conductive film 2 is not particularly limited, and examples thereof include a coating method, a sputtering method, a vacuum deposition method, a spray pyrolysis method, a chemical vapor deposition method (CVD), and a sol-gel method.
  • the oxide semiconductor porous film 3 is obtained by applying a dispersion of oxide semiconductor fine particles on the transparent conductive film 2.
  • oxide semiconductor fine particles include titanium oxide, tin oxide, zinc oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, vanadium oxide, niobium oxide, and the like. You may use independently and may use 2 or more types together.
  • the dispersion is obtained by mixing the oxide semiconductor fine particles and the dispersion medium with a dispersing machine such as a sand mill, a bead mill, a ball mill, a three roll mill, a colloid mill, an ultrasonic homogenizer, a Henschel mixer, or a jet mill.
  • the dispersion is preferably obtained by mixing with a disperser and then subjected to ultrasonic treatment using an ultrasonic homogenizer or the like immediately before use (coating). By performing ultrasonic treatment immediately before use, the photoelectric conversion efficiency of the photoelectric conversion element of the present invention becomes better.
  • ionic liquid (A) is easily filled into the oxide semiconductor porous film formed using the dispersion liquid subjected to ultrasonic treatment immediately before use.
  • acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, or the like may be added to the dispersion. Therefore, a polymer such as polyethylene oxide and polyvinyl alcohol, a cellulose-based thickener, or the like may be added.
  • dispersion examples include titanium oxide pastes SP100 and SP200 (both manufactured by Showa Denko KK), titanium oxide fine particles Ti-Nanoxide® T (manufactured by Solaronics), Ti-Nanoxide® D (manufactured by Solaronics), Ti-Nanoxide®T / SP (manufactured by Solaronics), Ti-Nanoxide® D / SP (manufactured by Solaronics), titania coating paste PECC01 (manufactured by Pexel Technologies), titania particle paste PST-18NR (JGC Catalysts & Chemicals), titania particle paste PST400C Commercial products such as (JGC catalyst conversion) can also be used.
  • a known wet film forming method can be used as a method for applying the dispersion on the transparent conductive film.
  • a known wet film forming method can be used.
  • Specific examples of the wet film forming method include a screen printing method, an ink jet printing method, a roll coating method, a doctor blade method, a spin coating method, and a spray coating method.
  • heat treatment for the purpose of improving electronic contact between the fine particles, improving adhesion with the transparent conductive film, and improving film strength, heat treatment, chemical treatment, plasma, It is preferable to perform ozone treatment or the like.
  • the temperature of the heat treatment is preferably 40 ° C. to 700 ° C., and preferably 40 ° C. to 650 ° C.
  • the heat treatment time is not particularly limited, but is usually about 10 seconds to 24 hours.
  • Specific examples of the chemical treatment include chemical plating treatment using a titanium tetrachloride aqueous solution, chemical adsorption treatment using a carboxylic acid derivative, and electrochemical plating treatment using a titanium trichloride aqueous solution.
  • the counter electrode is an electrode 5 disposed to face the photoelectrode 4.
  • a metal substrate a glass substrate having a conductive film on the surface, a resin substrate, or the like can be used.
  • metal substrate metals such as platinum, gold, silver, copper, aluminum, indium, and titanium can be used.
  • resin substrate in addition to the substrate (film) exemplified as the transparent substrate 1 constituting the photoelectrode 4, a general resin substrate which is opaque or inferior in transparency can also be used.
  • metals such as platinum, gold, silver, copper, aluminum, indium and titanium; carbon; tin oxide; tin oxide doped with antimony and fluorine; zinc oxide; doped with aluminum and gallium Zinc oxide; indium oxide doped with tin; conductive metal oxides such as;
  • the thickness and formation method of the conductive film can be the same as those of the transparent conductive film 2 constituting the photoelectrode 4.
  • the counter electrode 5 may be an electrode in which a conductive polymer film is formed on a substrate or a conductive polymer film electrode.
  • the conductive polymer include polythiophene, polypyrrole, polyaniline, and the like.
  • a method for forming a conductive polymer film on a substrate a conductive polymer film is formed on a substrate from a polymer dispersion using a dipping method, a spin coating method, or the like that is usually known as a wet film formation method. be able to.
  • Examples of the conductive polymer dispersion include the polyaniline dispersion disclosed in JP-A-2006-169291, a commercially available polythiophene derivative aqueous dispersion (Vitron P, manufactured by Bayer), Mitsubishi Rayon Co., Ltd. (Aqua Save, polyaniline). Derivative aqueous solution) and the like can be used.
  • a conductive polymer film can be formed on the substrate by an electrolytic polymerization method in addition to the above method.
  • Conductive polymer film electrode is a casting that is usually known as a wet film-forming method from a self-supporting film or a conductive polymer dispersion obtained by peeling off a conductive polymer film formed on an electrode by electrolytic polymerization. It is also possible to use a self-supporting film formed using a method or a spin coating method.
  • the conductive polymer dispersion referred to here is a conductive polymer dispersion in which conductive polymer fine particles are dispersed in a solvent and a conductive polymer is dissolved in a solvent. A functional polymer dispersion.
  • the electrolyte layer is an electrolyte layer 6 provided between the photoelectrode 4 and the counter electrode 5, and the above-described electrolyte of the present invention is used in the photoelectric conversion element of the present invention.
  • the photoelectric conversion element of the present invention uses the above-described electrolyte of the present invention, high energy conversion efficiency can be achieved without substantially containing iodine.
  • the dye-sensitized solar cell of the present invention is a kind of photoelectric conversion element in which a photosensitizing dye is supported on the photoelectrode constituting the photoelectric conversion element of the present invention described above.
  • the photosensitizing dye is not particularly limited as long as it is a dye having absorption in the visible light region and / or the infrared light region, and a metal complex, an organic dye, or the like can be used.
  • a ruthenium complex dye, a porphyrin dye, a phthalocyanine dye, a cyanine dye, a merocyanine dye, a xanthene dye or the like coordinated with a ligand such as a bipyridine structure or a terpyridine structure can be used.
  • the dye is dissolved in, for example, water or alcohol, and the oxide semiconductor porous film 3 is immersed in the dye solution or the dye solution is applied to the oxide semiconductor porous film 3. It is supported by.
  • a titanium oxide paste Ti-Nanoxide D (manufactured by Solaronix) is applied onto transparent conductive glass (FTO glass, surface resistance 15 ⁇ / ⁇ , manufactured by Nippon Sheet Glass Co., Ltd.), dried at room temperature, and then heated to 450 ° C. Was sintered for 30 minutes to produce a photoelectrode in which a porous titanium oxide film was formed on transparent conductive glass.
  • the produced photoelectrode was converted into a ruthenium complex dye (cis- (dithiocyanate) -N, N′-bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) complex) (Ruthenium). It was immersed in an ethanol solution (concentration 3 ⁇ 10 ⁇ 4 mol / L) of 535-bisTBA (manufactured by Solaronix) for 4 hours. Then, it wash
  • the electrolyte prepared above is applied on the photoelectrode carrying the photosensitizing dye, and this is and a transparent conductive glass substrate (indium oxide doped with tin on the conductive surface, sheet resistance: 8 ⁇ / ⁇ , manufactured by Nippon Sheet Glass Co., Ltd.)
  • a dye-sensitized solar cell was obtained by pasting a platinum counter electrode having a platinum thin film having a thickness of about 100 nm formed on the surface thereof by sputtering and fixing it with a clip.
  • the photoelectric conversion efficiency of the obtained dye-sensitized solar cell was measured and evaluated by the following method. The results are shown in Table 1.
  • ⁇ Photoelectric conversion efficiency> As shown in FIG. 2, a solar simulator is used as a light source, and AM1.5 simulated sunlight is irradiated from the photoelectrode side with a light intensity of 100 mW / cm 2 , and a current-voltage measuring device (Digital Source Meter 2400 manufactured by Keithley Instruments Co., Ltd.). ) To determine the conversion efficiency.
  • Each component in Table 1 is as follows.
  • Ionic liquid A1 1-methyl-3-propylimidazolium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Carbon material B1 Activated carbon (NY1151, specific surface area: 1325 m 2 / g, primary average particle size: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ ⁇ cm, manufactured by Kuraray Chemical Co., Ltd.)
  • Carbon material B2 activated carbon (NK261, specific surface area: 2300 m 2 / g, primary average particle diameter: 5 ⁇ m, specific resistance: 1.5 ⁇ 10 ⁇ 1 ⁇ ⁇ cm, manufactured by Kuraray Chemical Co., Ltd.)
  • Carbon material C1-1 Acetylene black (denka black powder, specific surface area: 68 m 2 / g, primary average particle size: 35 nm, specific resistance: 3 ⁇ 10 ⁇ 2 ⁇ ⁇ cm, manufactured by Denki Kagaku Kogyo Co., Ltd.
  • the electrolytes of Examples 1 to 5 prepared so as to contain the ionic liquid (A) and the carbon material (B) in specific ratios substantially contain iodine. Even without this, the photoelectric conversion efficiency was found to be sufficiently high at 4.3 to 4.9%. This is an unexpected result showing that it is superior to the electrolytes of Comparative Examples 3 to 7 prepared using acetylene black which is a conductive material.
  • the electrolytes of Examples 6 to 32 prepared so as to contain the ionic liquid (A) and the carbon material (B) at a specific ratio and further contain the carbon material (C) substantially contain iodine. Even if it does not contain, it turned out that photoelectric conversion efficiency becomes high enough with 5.0% or more.
  • the electrolytes of Examples 10 and 15 prepared using boron-modified acetylene black as the carbon material (C) have an even higher photoelectric conversion efficiency of 6.0% or more even when substantially free of iodine. It can be seen that the electrolytes of Examples 19 to 28 prepared using acidic carbon black as the carbon material (C) have a sufficiently high photoelectric conversion efficiency of 5.5% or more even when substantially free of iodine. I understood that.
  • the total content of the carbon material (B) and the carbon material (C) is 10 to 50 parts by mass with respect to 100 parts by mass of the ionic liquid (A).
  • electrolytes of Examples 33 and 34 prepared so as to contain the ionic liquid (A) and the carbon material (B) at a specific ratio and further contain silicon oxide or titanium oxide are substantially free of iodine.
  • the photoelectric conversion efficiency was found to be sufficiently high at 5.9% or more.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
PCT/JP2009/069981 2008-11-27 2009-11-26 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池 WO2010061901A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2010513520A JP4557097B2 (ja) 2008-11-27 2009-11-26 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
US13/131,674 US8338692B2 (en) 2008-11-27 2009-11-26 Electrolyte for photoelectric conversion elements, and photoelectric conversion element and dye-sensitized solar cell using the electrolyte
CN200980147543.3A CN102227847B (zh) 2008-11-27 2009-11-26 光电转换元件用电解质以及使用了该电解质的光电转换元件和染料敏化太阳能电池
DE112009003578.7T DE112009003578B4 (de) 2008-11-27 2009-11-26 Elektrolyt für photoelektrische Umwandlungselemente sowie photoelektrisches Umwandlungselement und farbstoffsensibilisierte Solarzelle, die den Elektrolyt verwendet

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2008302935 2008-11-27
JP2008-302935 2008-11-27
JP2008-312336 2008-12-08
JP2008312336 2008-12-08
JP2009-172351 2009-07-23
JP2009172351 2009-07-23

Publications (1)

Publication Number Publication Date
WO2010061901A1 true WO2010061901A1 (ja) 2010-06-03

Family

ID=42225772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/069981 WO2010061901A1 (ja) 2008-11-27 2009-11-26 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池

Country Status (4)

Country Link
JP (1) JP4557097B2 (de)
CN (1) CN102227847B (de)
DE (1) DE112009003578B4 (de)
WO (1) WO2010061901A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2256764A3 (de) * 2009-05-28 2011-09-14 TDK Corporation Farbstoffsensibilisierte Solarzelle und organisches, lösungsmittelfreies Elektrolyt für farbstoffsensibilisierte Solarzelle
JP7517098B2 (ja) 2020-11-13 2024-07-17 ａｒｔｉｅｎｃｅ株式会社 ホウ素含有多孔質炭素

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010074237A1 (ja) * 2008-12-26 2010-07-01 横浜ゴム株式会社 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
TWI466140B (zh) * 2011-11-23 2014-12-21 Ind Tech Res Inst 透明導電膜與其形成方法
CN107527999B (zh) * 2017-08-25 2020-03-31 京东方科技集团股份有限公司 半导体混合材料及其制备方法、薄膜晶体管以及电子装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007227087A (ja) * 2006-02-22 2007-09-06 Toin Gakuen 色素増感型光電変換素子
JP2008130537A (ja) * 2006-11-17 2008-06-05 Samsung Sdi Co Ltd 染料感応太陽電池用高分子ゲル電解質組成物、染料感応太陽電池及び染料感応太陽電池の製造方法
JP2009238693A (ja) * 2008-03-28 2009-10-15 Sumitomo Chemical Co Ltd 光電変換素子およびその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003231536B2 (en) * 2002-05-20 2006-01-12 Ecole Polytechnique Federale De Lausanne (Epfl) Photoelectric conversion device
JP4041409B2 (ja) 2003-02-05 2008-01-30 独立行政法人科学技術振興機構 多環式芳香族炭素系固体強酸
AU2004256669C1 (en) 2003-07-14 2009-09-24 Fujikura Ltd. Electrolyte composition, and photoelectric converter and dye-sensitized solar cell using same
JP2006169291A (ja) 2004-12-13 2006-06-29 Yokohama Rubber Co Ltd:The 変性導電性高分子並びにそれを用いた導電性部材
JP2010009831A (ja) * 2008-06-25 2010-01-14 Tdk Corp 光電変換素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007227087A (ja) * 2006-02-22 2007-09-06 Toin Gakuen 色素増感型光電変換素子
JP2008130537A (ja) * 2006-11-17 2008-06-05 Samsung Sdi Co Ltd 染料感応太陽電池用高分子ゲル電解質組成物、染料感応太陽電池及び染料感応太陽電池の製造方法
JP2009238693A (ja) * 2008-03-28 2009-10-15 Sumitomo Chemical Co Ltd 光電変換素子およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2256764A3 (de) * 2009-05-28 2011-09-14 TDK Corporation Farbstoffsensibilisierte Solarzelle und organisches, lösungsmittelfreies Elektrolyt für farbstoffsensibilisierte Solarzelle
JP7517098B2 (ja) 2020-11-13 2024-07-17 ａｒｔｉｅｎｃｅ株式会社 ホウ素含有多孔質炭素

Also Published As

Publication number Publication date
JPWO2010061901A1 (ja) 2012-04-26
DE112009003578T5 (de) 2012-04-26
JP4557097B2 (ja) 2010-10-06
CN102227847A (zh) 2011-10-26
CN102227847B (zh) 2014-07-02
DE112009003578B4 (de) 2014-11-27

Similar Documents

Publication Publication Date Title
Huo et al. High performance sponge-like cobalt sulfide/reduced graphene oxide hybrid counter electrode for dye-sensitized solar cells
Miyasaka et al. Photovoltaic performance of plastic dye-sensitized electrodes prepared by low-temperature binder-free coating of mesoscopic titania
EP1653549B1 (de) Fotoelektrisches umwandlungselement und farbstoffsensibilisierte solarzelle
JP4725689B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
US20110056563A1 (en) Electrolyte composition
JP4692694B2 (ja) 色素増感太陽電池用電解質およびその電解質を用いた色素増感太陽電池
JP4557097B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
TW200933957A (en) Electrolyte composition and photoelectric conversion element using the same
JP5019007B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
JP5177318B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
Fang et al. A novel thixotropic and ionic liquid-based gel electrolyte for efficient dye-sensitized solar cells
WO2011114915A1 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
US8338692B2 (en) Electrolyte for photoelectric conversion elements, and photoelectric conversion element and dye-sensitized solar cell using the electrolyte
JP2010262817A (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
JP5598068B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
JP2011054314A (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
WO2010061663A1 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
JP6019688B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池
JP2011243310A (ja) 光電変換素子用電解質、光電変換素子、および、色素増感太陽電池
JP6003175B2 (ja) 光電変換素子用電解質ならびにその電解質を用いた光電変換素子および色素増感太陽電池

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980147543.3

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2010513520

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09829146

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13131674

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 09829146

Country of ref document: EP

Kind code of ref document: A1