WO2009154274A1 - 酸化チタン構造体及び多孔質酸化チタン組成物 - Google Patents
酸化チタン構造体及び多孔質酸化チタン組成物 Download PDFInfo
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- WO2009154274A1 WO2009154274A1 PCT/JP2009/061220 JP2009061220W WO2009154274A1 WO 2009154274 A1 WO2009154274 A1 WO 2009154274A1 JP 2009061220 W JP2009061220 W JP 2009061220W WO 2009154274 A1 WO2009154274 A1 WO 2009154274A1
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- WIPO (PCT)
- Prior art keywords
- titanium oxide
- carbon
- nanoscale carbon
- particulate
- structure according
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C01—INORGANIC CHEMISTRY
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Definitions
- the present invention relates to a titanium oxide composite used for a photoelectric conversion element such as a dye-sensitized solar cell and a production method thereof, a porous titanium oxide composition and a production method thereof, and the titanium oxide composite and the porous titanium oxide composition.
- the present invention relates to a photoelectric conversion element using an object.
- Solar cells are attracting attention as environmentally friendly power generation devices, and silicon-based semiconductors using pn junctions are widely known.
- silicon-based solar cells require a high vacuum and a high temperature during production, and it is difficult to reduce the cost, which has hindered their spread.
- titanium oxide nanoparticles exhibit high performance as an active electrode.
- the reason why the nanoparticles are used is that the incident light can be efficiently absorbed by using a large area for guiding the dye to be adsorbed on the titanium oxide.
- the efficient movement of charge-separated electrons is hindered, or the distance between adjacent particles is close to each other, There was a trade-off relationship in which the movement of ions in the electrolyte solution near the nanoparticles became difficult and the movement of electrons associated therewith was inhibited.
- titanium oxide that achieves both efficient movement of electrons and ions has been demanded.
- nanowire-shaped titanium oxide as an active electrode
- examples using nanowire-shaped titanium oxide as an active electrode have also been reported (see Non-Patent Documents 1 and 2).
- nanowires composed only of titanium oxide having a smooth surface cannot carry a sufficient dye to absorb incident light, and an improvement in the density of generated current has been demanded.
- Patent Document 2 in order to improve the electron conduction in titanium oxide and efficiently transfer electrons from the titanium oxide to the electrode, the longitudinal direction is set to improve the conductivity of the current flowing in the film stacking direction.
- An active electrode having a structure in which titanium oxide is coated on tubular carbon oriented substantially perpendicular to the film-forming surface of the substrate has been studied. However, it is difficult to form a uniform titanium oxide film, which increases leakage current. There's a problem.
- Patent Document 3 mixing of the active material oxide particles and the nanocarbon tube is attempted. However, if the active material oxide is not sufficiently coated, the leakage current increases, and on the contrary, the power generation efficiency is increased. There is a problem of reduction.
- the present invention is based on the concept of realizing a titanium oxide structure having a large surface area and enabling efficient movement of ions and electrons, and a material effective as an active substance of a dye-sensitized solar cell, a method for producing the material, a porous oxidation It aims at developing a photoelectric conversion element using a titanium composition, its manufacturing method, and this titanium oxide structure or a porous titanium oxide composition.
- the present invention has the following configuration.
- Item 1 A rod-like, tubular or fibrous titanium oxide structure formed by continuous particulate titanium oxide.
- Item 2. The titanium oxide structure according to Item 1, wherein the particulate titanium oxide (1a) has an average particle size of 1 to 200 nm.
- Item 3 The titanium oxide structure according to Item 1 or 2, wherein the average diameter perpendicular to the major axis is 5 to 500 nm, the average length of the major axis is 0.1 to 1000 ⁇ m, and the average aspect ratio is 3 to 200,000.
- Item 4 The titanium oxide structure according to any one of Items 1 to 3, wherein the powder resistance under a pressure of 10 MPa is 3 ⁇ 10 6 ⁇ ⁇ m or less.
- Item 5. The titanium oxide structure according to any one of Items 1 to 4, which is tubular.
- Item 6 The titanium oxide structure according to Item 5, wherein the thickness is 2 to 500 nm.
- Item 7 The titanium oxide structure according to any one of Items 1 to 6, wherein the particulate titanium oxide (1a) contains at least one selected from the group consisting of anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide.
- the particulate titanium oxide (1a) is in addition to at least one selected from the group consisting of anatase-type titanium oxide, rutile-type titanium oxide and brookite-type titanium oxide, and further, bivalent titanium oxide and trivalent titanium oxide.
- Item 8 The titanium oxide structure according to Item 7, comprising at least one selected from the group consisting of products.
- Item 9 The titanium oxide structure according to any one of Items 1 to 8, wherein the particulate titanium oxide (1a) includes titanium oxide having a crystal form of a Magneli phase structure.
- Item 10 The titanium oxide structure according to any one of Items 1 to 9, wherein the specific surface area is 20 m 2 / g or more.
- Item 11 A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex, thereby producing a titanium oxide-coated nanoscale carbon.
- Process, Item 11. The method for producing a titanium oxide structure according to any one of Items 1 to 10, comprising a step of eliminating the nanoscale carbon present in the titanium oxide-coated nanoscale carbon.
- Item 12. The method for producing a titanium oxide structure according to Item 11, wherein the titanium oxide-coated nanoscale carbon is measured by electron microscope observation, and the titanium oxide coverage on the surface of the nanoscale carbon is 70 to 100%.
- Item 13 The method for producing a titanium oxide structure according to Item 11 or 12, wherein the titanium oxide-coated nanoscale carbon has a carbon / titanium surface element ratio of 0/100 to 70/30 (atomic ratio) by X-ray photoelectron spectroscopy.
- the average diameter perpendicular to the long axis of the rod-like or fibrous nanoscale carbon is 1 to 100 nm, the average length of the long axis is 0.1 to 1000 ⁇ m, and the average aspect ratio is 5 to 1000000.
- the manufacturing method of the titanium oxide structure in any one.
- Item 15 The method for producing a titanium oxide structure according to any one of Items 11 to 14, wherein the rod-like or fibrous nanoscale carbon is a nanoscale carbon tube.
- Item 16 A porous titanium oxide composition obtained by mixing the titanium oxide structure according to any one of Items 1 to 10 and (2) particulate titanium oxide.
- Item 17 The porous titanium oxide composition according to item 16, wherein 0.1 to 90% by weight of the titanium oxide structure (1) and 10 to 99.9% by weight of the particulate titanium oxide (2) are mixed.
- Item 18 The porous titanium oxide composition according to item 16 or 17, wherein the particulate titanium oxide (2) has an average particle diameter of 1 to 500 nm.
- Item 19 The porous titanium oxide composition according to any one of Items 16 to 18, wherein the particulate titanium oxide (2) contains at least one selected from the group consisting of anatase type titanium oxide, rutile type titanium oxide and brookite type titanium oxide. .
- Item 20 The porous titanium oxide composition according to any one of Items 16 to 19, wherein the specific surface area is 30 m 2 / g or more.
- Item 21 The porous titanium oxide composition according to any one of Items 16 to 20, wherein pores having a pore diameter of 5 to 50 nm are present in 40 to 100% of all pores.
- Item 22 A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex to produce a titanium oxide-coated nanoscale carbon.
- Process, (B1) The step of producing the titanium oxide structure (1) by eliminating the nanoscale carbon existing in the titanium oxide-coated nanoscale carbon obtained in the step (A1), and the step (C1) obtained in the step (B1).
- Item 22 The method for producing a porous titanium oxide composition according to any one of Items 16 to 21, comprising a step of mixing the obtained titanium oxide structure (1) and particulate titanium oxide (2).
- Item 23 A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex to produce a titanium oxide-coated nanoscale carbon.
- Process, (B2) The step of mixing the titanium oxide-coated nanoscale carbon obtained in the step (A2) and the particulate titanium oxide (2), and the (C2) titanium oxide-coated nanoparticle in the mixture obtained in the step (B2).
- Item 22 The method for producing a porous titanium oxide composition according to any one of Items 16 to 21, comprising a step of eliminating nanoscale carbon present in the scale carbon.
- Item 24 A photocatalyst comprising a dye supported on a surface of an active substance containing the titanium oxide structure according to any one of claims 1 to 10 or the porous titanium oxide composition according to any one of claims 16 to 21. Conversion element.
- a photoelectric conversion element using the quality titanium oxide composition can be provided.
- FIG. 6 is an electron microscope (TEM) photograph showing the presence of an iron-carbon composite in the carbonaceous material obtained in Example 1 of JP-A-2002-338220.
- 2 is an electron microscope (TEM) photograph in which one iron-carbon composite obtained in Example 1 of JP-A-2002-338220 is cut into a ring shape.
- delta)) shown in the photograph of FIG. 6 has shown the EDX measurement point for composition analysis.
- a schematic diagram of a TEM image of a carbon tube is shown, (a-1) is a schematic diagram of a TEM image of a cylindrical nanoflake carbon tube, and (a-2) is a TEM image of a multi-walled carbon nanotube with a nested structure
- FIG. 2 is an electron microscope (TEM) photograph of an end portion of the titanium oxide structure of Example 1.
- FIG. 2 is an electron microscope (TEM) photograph of the central portion of the titanium oxide structure of Example 1.
- Titanium oxide structure (1) The rod-like, tubular or fibrous titanium oxide structure (1) of the present invention is composed of continuous titanium oxide (1a).
- the titanium oxide structure (1) of the present invention is preferably a tubular one because it has a large surface area among rod-like, tubular and fibrous ones.
- continuous means that the particulate titanium oxide (1a) is in close contact with the adjacent titanium oxide (1a) and is not simply obtained by mixing.
- the particulate titanium oxide (1a) is continuously formed so as to form a rod-like, tubular or fibrous shape to form the titanium oxide structure (1).
- corrugation exists in the surface of the rod-shaped, tubular or fibrous titanium oxide structure (1) of this invention.
- the titanium oxide structure (1) having fine irregularities on the surface for a dye-sensitized solar cell a large amount of the dye is supported and incident light can be efficiently absorbed.
- electrons are efficiently generated, and as shown in FIG. 2, since the adjacent titanium oxides (1a) are in close contact with each other, the electrons are efficiently conveyed to the transparent electrode through the adjacent titanium oxide (1a). be able to.
- Particulate titanium oxide (1a) The crystal structure of the particulate titanium oxide (1a) is not particularly limited, but preferably includes at least one selected from the group consisting of anatase-type titanium oxide, rutile-type titanium oxide and brookite-type titanium oxide. From the viewpoint of high light activity, those containing anatase-type titanium oxide are more preferable.
- the crystal structure of the particulate titanium oxide (1a) can be measured by, for example, X-ray diffraction method, Raman spectroscopic analysis or the like.
- the particulate titanium oxide (1a) is selected from the group consisting of an oxide of divalent titanium and an oxide of trivalent titanium in addition to anatase type titanium oxide, rutile type titanium oxide and brookite type titanium oxide. It is preferable to contain at least one kind.
- the particulate titanium oxide (1a) includes titanium oxide having a crystal form of a Magneli phase structure.
- the specific structure of the titanium oxide having the crystal form of the magnetic phase structure is not clear, but is represented by the composition formula: Ti n O 2n-1 (n: 4 to 10), and has the same conductivity as that of the metal. It is what has. By including titanium oxide having a crystal form of this magnetic phase structure, the conductivity of the titanium oxide structure can be improved.
- the average particle diameter of the particulate titanium oxide (1a) is preferably 1 to 200 nm, more preferably 1 to 50 nm from the viewpoint that more dye can be adsorbed and light can be absorbed.
- titanium oxide particles having a large particle size and large light scattering may be mixed.
- an average particle diameter can be measured by electron microscope (SEM or TEM) observation etc., for example.
- Titanium oxide structure (1) Titanium oxide structure (1) of the present invention, dye was large amount of carrier, from the viewpoint of efficiently absorbing incident light, specific surface area is preferably not more 20 m 2 / g or more, a specific surface area of 70m 2 / What is more than g is more preferable, and what is more than 80 m ⁇ 2 > / g is further more preferable.
- the specific surface area is preferably larger, and the upper limit is not particularly limited, but is about 3000 m 2 / g.
- the specific surface area can be measured by the BET method or the like.
- the titanium oxide structure (1) of the present invention has a sufficient surface area and efficiently transmits electrons, so that the average diameter perpendicular to the major axis is 5 to 500 nm, and the average length of the major axis is 0.00.
- the average aspect ratio (average major axis length / average diameter perpendicular to the major axis) is 3 to 200,000, the average diameter perpendicular to the major axis is 5 to 500 nm, and the major axis average length More preferably, the average aspect ratio (average long axis / average diameter perpendicular to the long axis) is from 3 to 5000, and the average diameter orthogonal to the long axis is from 7 to 300 nm.
- the long axis has an average length of 1 to 50 ⁇ m and an average aspect ratio of 10 to 3000.
- the diameter means an outer diameter.
- the average diameter, average length, and average aspect ratio of the titanium oxide structure (1) can be measured, for example, by observation with an electron microscope (SEM).
- the titanium oxide structure (1) of the present invention preferably has a powder resistance of 3 ⁇ 10 6 ⁇ ⁇ m or less under 10 MPa from the viewpoint of obtaining a larger current, and 1 ⁇ 10 5 ⁇ ⁇ m.
- the powder resistance is preferably as small as possible, and the lower limit is not particularly limited, but is about 0.1 ⁇ ⁇ m.
- the method for measuring the powder resistance of the titanium oxide structure is not particularly limited. For example, the current value is processed by applying a voltage of 1 V between the pellets after processing into a plate having a thickness of 0.3 mm at a pressure of 10 MPa. It can be measured by measuring.
- the thickness of the titanium oxide structure (1) of the present invention is tubular, its thickness is preferably about 2 to 500 nm, more preferably about 5 to 200 nm from the viewpoint of preventing leakage current.
- the wall thickness means the difference between the outer diameter and the inner diameter of the tubular titanium oxide structure (1).
- the thickness of the titanium oxide structure (1) of the present invention can be measured, for example, by observation with an electron microscope (SEM or TEM).
- the titanium oxide structure (1) of the present invention is: (A) A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex, thereby producing a titanium oxide-coated nanoscale carbon. Process, (B) It is obtained by a process of eliminating nanoscale carbon existing in titanium oxide-coated nanoscale carbon.
- Step (A) In the step (A), a coating layer composed of continuous titanium oxide (1a) is formed on the surface of the rod-like or fiber-like nanoscale carbon by a precipitation reaction from a titanium fluoro complex, and the titanium oxide-coated nanoscale carbon is formed. Is made.
- a sol-gel method using titanium alkoxide as a raw material or a wet method using titanium tetrachloride as a raw material can form a coating layer in which particulate titanium oxide (1a) is continuous on the surface of nanoscale carbon.
- a method in which titanium oxide is precipitated by a precipitation reaction from a fluoro complex is preferred.
- rod-like or fibrous nanoscale carbon is treated with an acid such as nitric acid, sulfuric acid, hydrochloric acid, etc., and then dispersed in a solvent containing a dispersant.
- a fluoride ion scavenger such as aluminum is added to deposit titanium oxide (1a).
- the titanium fluoro complex is not particularly limited, and examples thereof include ammonium hexafluorotitanate, hexafluorotitanate, and potassium hexafluorotitanate.
- the solvent is not particularly limited, and examples thereof include water, a mixed solvent of water and alcohol, and a solvent in which the titanium fluoro complex is dissolved.
- dispersant examples include anionic dispersions such as sodium naphthalene sulfonate formalin condensate-based dispersant, polycarboxylate-based dispersant, maleic acid ⁇ -olefin copolymer salt-based dispersant, and anionic surfactant.
- Agents Cationic dispersants such as quaternary ammonium salt dispersants and alkylamine salts; Nonionic dispersants such as cellulose dispersants, polyvinyl alcohol dispersants, polyether dispersants; amphoteric surfactants, etc. Other dispersants and the like. Among these, nonionic dispersants are preferable, and polyether dispersants are more preferable.
- nanoscale carbon that can be used in the step (A) will be described in detail below.
- Nanoscale carbon Although there is no restriction
- the nanoscale carbon tube is preferably formed of a conductive material.
- this rod-like or fibrous nano-scale carbon has an average diameter of about 1 to 100 nm perpendicular to the major axis because it can produce a structure that is as fine as possible and has a large surface area and can be continuously long and continuous with titanium oxide (1a).
- the average length of the major axis is preferably about 0.1 to 1000 ⁇ m and the average aspect ratio is about 5 to 1,000,000, the average diameter orthogonal to the major axis is about 1 to 100 nm, and the average length of the major axis is about 0.1.
- the average aspect ratio is about 1 to 1000 ⁇ m, the average aspect ratio is about 5 to 10,000, the average diameter orthogonal to the major axis is about 1 to 50 nm, the average length of the major axis is about 1 to 50 ⁇ m, and the average aspect ratio is 10 to 10 More preferred is about 10,000.
- the average diameter orthogonal to the long axis, the average length of the long axis, and the average aspect ratio can be measured, for example, by observation with an electron microscope (SEM or TEM).
- Nanoscale carbon tube The nanoscale carbon tube that can be used in the present invention refers to a carbon tube having a nano-sized diameter, and iron or the like may be included in the inner space of the carbon tube.
- nanoscale carbon tube As such a nanoscale carbon tube, (I) single-walled carbon nanotubes or multi-walled carbon nanotubes, (II) an amorphous nanoscale carbon tube developed by the present applicant, (III) Nano flake carbon tube, (IV) (a) a carbon tube selected from the group consisting of nano-flake carbon tubes and nested multi-walled carbon nanotubes and (b) iron carbide or iron, and 10 of the space in the tube of the carbon tube (a) An iron-carbon composite filled with iron carbide or iron of (b) in a range of ⁇ 90%; (V) These 2 or more types of mixtures etc. can be illustrated.
- the carbon nanotube (I) is a hollow carbon material in which a graphite sheet (that is, a carbon atom plane or graphene sheet having a graphite structure) is closed like a tube, its diameter is nanometer scale, and the wall structure has a graphite structure. is doing.
- a graphite sheet that is, a carbon atom plane or graphene sheet having a graphite structure
- the wall structure has a graphite structure. is doing.
- the carbon nanotubes (I) those whose wall structure is closed in a tube shape with a single graphite sheet are called single-walled carbon nanotubes, and each of a plurality of graphite sheets is closed in a tube shape and is nested. What is present is called a nested multi-walled carbon nanotube.
- both of these single-walled carbon nanotubes and nested multi-walled carbon nanotubes can be used.
- the single-walled carbon nanotube that can be used in the present invention has an average diameter orthogonal to the major axis of about 1 to 10 nm, an average length of the major axis of about 0.1 to 500 ⁇ m, and an average aspect ratio of about 10 to 500,000. More preferably, the average diameter orthogonal to the major axis is about 1 to 10 nm, the average length of the major axis is about 0.1 to 500 ⁇ m, and the average aspect ratio is about 10 to 50,000. Is more preferably about 1 to 5 nm, the average length of the major axis is about 1 to 100 ⁇ m, and the average aspect ratio is about 15 to 30000. In particular, the average diameter perpendicular to the major axis is about 1 to 2 nm. Those having an average length of about 1 to 20 ⁇ m and an average aspect ratio of about 20 to 20000 are preferable.
- the nested multi-walled carbon nanotube that can be used in the present invention has an average diameter orthogonal to the major axis of about 1 to 100 nm, an average length of the major axis of about 0.1 to 500 ⁇ m, and an average aspect ratio of 1 to 500,000. More preferably, the average diameter orthogonal to the major axis is about 1 to 100 nm, the average length of the major axis is about 0.1 to 500 ⁇ m, and the average aspect ratio is about 5 to 10,000.
- the average diameter orthogonal to the major axis is about 1 to 50 nm
- the average length of the major axis is about 1 to 100 ⁇ m
- the average aspect ratio is about 10 to 10,000
- the average diameter perpendicular to the major axis is particularly about 1 to 40 nm.
- the long axis has an average length of about 1 to 20 ⁇ m and an average aspect ratio of about 10 to 10,000.
- Amorphous nanoscale carbon tube > An amorphous nanoscale carbon tube (II) is described in WO 00/40509 (Japanese Patent No. 3355442), has a main skeleton made of carbon, has a diameter of 0.1 to 1000 nm, and has an amorphous structure.
- the amorphous nanoscale carbon tube (II) is a thermally decomposable resin having a decomposition temperature of 200 to 900 ° C. in the presence of a catalyst composed of at least one metal chloride such as magnesium, iron, cobalt, and nickel.
- a catalyst composed of at least one metal chloride such as magnesium, iron, cobalt, and nickel.
- it can be obtained by exciting polytetrafluoroethylene, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol or the like.
- the shape of the thermally decomposable resin as a starting material may be any shape such as a film shape, a sheet shape, a powder shape, or a lump shape.
- excitation treatment may be performed under appropriate conditions with a thermally decomposable resin applied or placed on the substrate. .
- heating is performed in an inert atmosphere, preferably in a temperature range of about 450 to 1800 ° C. and higher than the thermal decomposition temperature of the raw material, and in a temperature range of about room temperature to 3000 ° C. and the thermal decomposition temperature of the raw material.
- the process of plasma processing etc. can be illustrated by the above.
- the amorphous nanoscale carbon tube (II) that can be used in the present invention is a nanoscale carbon nanotube having an amorphous structure (amorphous structure), has a hollow linear shape, and has a highly controlled pore.
- the shape is mainly a cylinder, a quadrangular prism, etc., and at least one of the tips often has no cap (open). When the tip is closed, the shape is often flat.
- the amorphous nanoscale carbon tube (II) preferably has an average outer diameter of about 1 to 100 nm, an average length of about 0.1 to 1000 ⁇ m, an average aspect ratio of about 1 to 1000000, and an average outer diameter of 1 More preferably, the average length is about 100 nm, the average length is about 0.1 to 1000 ⁇ m, the average aspect ratio is about 5 to 10,000, the average outer diameter is about 1 to 50 nm, the average length is about 1 to 50 ⁇ m, and the average aspect ratio Is more preferably about 10 to 10,000.
- amorphous structure means a carbonaceous structure consisting of an irregular carbon network plane, not a graphite structure consisting of a continuous carbon layer of regularly arranged carbon atoms.
- the graphene sheets are irregularly arranged.
- the nanoscale carbon tube having an amorphous structure that can be used in the present invention has a planar spread of the carbon network plane of the amorphous nanoscale carbon tube (II). Less than 1 times the diameter.
- the amorphous nanoscale carbon tube (II) has an amorphous structure in which a large number of fine graphene sheets (carbon network surface) are irregularly distributed instead of a graphite structure on the wall portion. Is not continuous over the entire length in the tube longitudinal direction, but is discontinuous.
- the length of the carbon network surface constituting the outermost layer is less than 20 nm, particularly less than 5 nm.
- Amorphous carbon generally does not exhibit X-ray diffraction, but exhibits broad reflection.
- an amorphous structure generally does not exhibit X-ray diffraction as described above, but partially exhibits very weak coherent scattering.
- the carbon mesh plane spacing (d 002 ) is 3.54 mm or more, more preferably 3.7 mm or more; the diffraction angle (2 ⁇ ) is 25.1 degrees or less, more preferably 24.1 degrees or less.
- the half width of the 2 ⁇ band is 3.2 degrees or more, more preferably 7.0 degrees or more.
- the amorphous nanoscale carbon tube (II) that can be used in the present invention has a diffraction angle (2 ⁇ ) by X-ray diffraction in the range of 18.9 to 22.6 degrees, and the carbon network plane spacing (d 002 ) is in the range of 3.9 to 4.7 mm, and the half width of the 2 ⁇ band is in the range of 7.6 to 8.2 degrees.
- linear which is one term representing the shape of the amorphous nanoscale carbon tube (II) that can be used in the present invention, is defined as follows. That is, when the length of a transmission electron microscope according amorphous nanoscale carbon tubes (II) image is L, the length of time that extended the amorphous nanoscale carbon tubes (II) was L 0, L / L It shall mean a shape characteristic in which 0 is 0.9 or more.
- the tube wall portion of the amorphous nanoscale carbon tube (II) has an amorphous structure composed of a plurality of fine carbon network planes (graphene sheets) oriented in all directions. It has an advantage that it has an active point or is excellent in affinity with the resin.
- Iron-carbon composite An iron-carbon composite (IV) that can be used in the present invention is described in JP-A-2002-338220 (Patent No. 3569806), and (a) a nano-flake carbon tube and a multi-layer carbon nanotube having a nested structure And a carbon tube selected from the group consisting of (b) iron carbide or iron, and 10 to 90% of the space in the tube of the carbon tube (a) is filled with the iron carbide or iron of (b). ing. That is, 100% of the space in the tube is not completely filled, and the iron carbide or iron is filled in the range of 10 to 90% of the space in the tube (that is, partially filled). It is characterized in that it is filled in).
- the wall portion is a patchwork-like or machete-like (so-called paper match-like) nanoflake carbon tube.
- the “nano flake carbon tube” is a graphite sheet composed of a plurality of (usually many) flake-like graphite sheets assembled in a patchwork or papier-like (paper machete) shape. It refers to a carbon tube made of aggregate.
- Such an iron-carbon composite (IV) is obtained by the method described in JP-A-2002-338220.
- an inert gas in the reaction furnace And a heat decomposable carbon source is introduced at a pressure of 10 ⁇ 5 Pa to 200 kPa, and a heat treatment is performed at 600 to 900 ° C.
- Ncc which is a unit of the oxygen amount B, means a volume (cc) when converted into a standard state of gas at 25 ° C.
- the iron-carbon composite (IV) is composed of (a) a carbon tube selected from the group consisting of nano-flake carbon tubes and nested multi-walled carbon nanotubes, and (b) iron carbide or iron,
- the space inside the carbon tube (that is, the space surrounded by the tube wall) is not completely filled, but a part of the space, more specifically about 10 to 90%, especially 30 to About 80%, preferably about 40 to 70%, is filled with iron carbide or iron.
- the carbon portion is identified after the production steps (1) and (2). When it is cooled at a speed of, it becomes a nano flake carbon tube, and after performing manufacturing steps (1) and (2), heat treatment is performed in an inert gas, and cooling is performed at a specific cooling speed, thereby nesting the multilayer carbon. It becomes a nanotube.
- nano-flake carbon tube (a-1) that can be used in the present invention and the iron-carbon composite (IV) composed of iron carbide or iron (b) are typically cylindrical, but such cylindrical
- TEM transmission electron microscope
- FIG. 7 shows a schematic diagram of a TEM image of such a columnar nano-flake carbon tube.
- 100 schematically shows a TEM image in the longitudinal direction of the nanoflake carbon tube
- 200 shows a TEM image in a cross section substantially perpendicular to the longitudinal direction of the nanoflake carbon tube. This is shown schematically.
- the nanoflake carbon tube (a-1) constituting the iron-carbon composite (IV) that can be used in the present invention typically has a hollow cylindrical shape, and when its cross section is observed by TEM, it is arc-shaped.
- the graphene sheet images are concentrically assembled, and each graphene sheet image forms a discontinuous ring. When the longitudinal direction is observed with a TEM, the substantially straight graphene sheet image is The graphene sheet images are not continuous over the entire length in the longitudinal direction but are discontinuous.
- the nanoflake carbon tube (a-1) constituting the iron-carbon composite (IV) that can be used in the present invention is apparent from 200 in FIGS. 6 and 7 (a-1).
- a large number of arc-shaped graphene sheet images are concentrically (multi-layered tube shape).
- a continuous ring that is completely closed is not formed, but a discontinuous ring that is interrupted is formed.
- Some graphene sheet images may be branched as indicated by 211.
- a plurality of arc-shaped TEM images constituting one discontinuous ring may have a partially disturbed layer structure as indicated by 222 in FIG.
- the iron-carbon composites (IV) that can be used in the present invention are arranged in multiple layers almost in parallel with the longitudinal direction of the iron-carbon composites (IV). It is not continuous and is discontinuous along the way.
- Some graphene sheet images may be branched as indicated by reference numeral 111 in FIG.
- a TEM image of one discontinuous layer is at least partly adjacent to the adjacent graphene sheet image as indicated by 112 in FIG. In some cases, they may overlap each other or may be slightly separated from adjacent graphene sheet images as indicated by 113, but a large number of substantially linear TEM images form a multilayer structure as a whole.
- the structure of the nano flake carbon tube (a-1) that can be used in the present invention is greatly different from the conventional multi-walled carbon nanotube. That is, as shown by 400 in FIG. 7A-2, the multi-walled carbon nanotube (a-2) having a nested structure has a TEM image of a cross section perpendicular to the longitudinal direction substantially as shown by 410. As shown by 300 in FIG. 7 (a-2), a straight graphene sheet image 310, etc., which is a concentric tube that is a complete circular TEM image, is continuous over the entire length in the longitudinal direction. It is a structure arranged in parallel (concentric cylindrical or nested structure).
- the nano-flake carbon tube (a-1) constituting the iron-carbon composite (IV) that can be used in the present invention is patched with a large number of flake-like graphene sheets. It seems that it forms a tube as a whole by overlapping in the shape of a workpiece or papier.
- Such a nano-flake carbon tube (a-1) that can be used in the present invention and an iron-carbon composite (IV) composed of iron carbide or iron (b) contained in the space in the tube is disclosed in Japanese Patent No. 2546114.
- the structure of the carbon tube is greatly different from that of the composite in which the metal is included in the inner space of the tube of the nested multi-walled carbon nanotube (a-2) as described in (1).
- the length of each graphene sheet image is usually about 2 to 500 nm, particularly about 10 to 100 nm. That is, as indicated by 100 in (a-1) of FIG. 7, a large number of TEM images of the substantially linear graphene sheet indicated by 110 are gathered to obtain a TEM image of the wall portion of the nanoflake carbon tube (a-1).
- the length of each substantially linear graphene sheet image is usually about 2 to 500 nm, particularly about 10 to 100 nm.
- the outermost layer of the nanoflake carbon tube (a-1) constituting the wall portion is a discontinuous graphene sheet that is not continuous over the entire length in the tube longitudinal direction.
- the length of the outermost carbon network surface is usually about 2 to 500 nm, particularly about 10 to 100 nm.
- the carbon portion of the wall portion of the nano-flake carbon tube (a-1) constituting the iron-carbon composite (IV) that can be used in the present invention has a large number of flake-like graphene sheets oriented in the longitudinal direction as described above. Although it has a tube shape as a whole, it has a graphitic structure with an average distance (d 002 ) between carbon network surfaces of 0.34 nm or less when measured by an X-ray diffraction method.
- the thickness of the wall portion made of the nano-flake carbon tube (a-1) of the iron-carbon composite (IV) that can be used in the present invention is 49 nm or less, particularly about 0.1 to 20 nm, preferably 1 to 10 nm. And is substantially uniform over the entire length.
- the carbon tube constituting the iron-carbon composite (IV) obtained by performing the specific heating step after performing the steps (1) and (2) is a multi-layer carbon nanotube having a nested structure. (A-2).
- a TEM image of a cross section perpendicular to the longitudinal direction forms a substantially perfect circle as indicated by 400 in FIG. 7 (a-2).
- a graphene sheet image that is continuous over the entire length in the longitudinal direction thereof is arranged in parallel (a concentric cylindrical or nested structure).
- the carbon portion of the wall portion of the multi-walled carbon nanotube (a-2) of the nested structure constituting the iron-carbon composite (IV) that can be used in the present invention is measured between the carbon network surfaces when measured by an X-ray diffraction method.
- the average distance (d 002 ) has a graphite structure of 0.34 nm or less.
- the thickness of the wall portion made of the multi-walled carbon nanotube (a-2) of the iron-carbon composite (IV) nested structure that can be used in the present invention is 49 nm or less, particularly about 0.1 to 20 nm, preferably 1 It is about ⁇ 10 nm and is substantially uniform over the entire length.
- the filling ratio of the space inside the carbon tube selected from the group consisting of the nano flake carbon tube (a-1) and the nested multi-walled carbon nanotube (a-2) with iron carbide or iron (b) ( 10-90%) observed the iron-carbon composite (IV) that can be used in the present invention with a transmission electron microscope, and the space of each carbon tube (that is, the space surrounded by the tube wall of the carbon tube). It is the ratio of the area of the image of the portion filled with iron carbide or iron (b) to the area of the image.
- the iron-carbon composite (IV) that can be used in the present invention should be referred to as a metal-encapsulated carbon complex, an iron compound-encapsulated carbon complex, iron carbide, or an iron-encapsulated carbon complex.
- the iron carbide or iron (b) included in the iron-carbon composite (IV) that can be used in the present invention is oriented in the longitudinal direction of the carbon tube, has high crystallinity, and has high crystallinity.
- the ratio of the area of the TEM image of crystalline iron carbide or iron (b) to the area of the TEM image in the range filled with b) (hereinafter referred to as “crystallization rate”) is generally about 90 to 100%, In particular, it is about 95 to 100%.
- the high crystallinity of the encapsulated iron carbide or iron (b) indicates that the TEM images of the inclusions are arranged in a lattice pattern when observed from the side of the iron-carbon composite (IV) that can be used in the present invention. This is clear from the fact that a clear diffraction pattern is obtained in electron beam diffraction.
- iron carbide or iron (b) is included in the iron-carbon composite (IV) that can be used in the present invention. Can do.
- the iron-carbon composite (IV) that can be used in the present invention has little curvature and is linear, and the wall portion has a substantially uniform thickness over the entire length. And has a homogeneous shape.
- the shape is columnar and mainly cylindrical.
- the iron-carbon composite (IV) preferably has an average outer diameter of about 1 to 100 nm, an average length of about 0.1 to 1000 ⁇ m, an average aspect ratio of about 1 to 1000000, and an average outer diameter of 1 More preferable is about 100 nm, average length is about 0.1 to 1000 ⁇ m, average aspect ratio is about 5 to 10,000, average outer diameter is about 1 to 50 nm, average length is about 1 to 400 ⁇ m, average aspect ratio Is more preferably about 10 to 10,000.
- linear which is one term representing the shape of the iron-carbon composite (IV) that can be used in the present invention, is defined as follows. That is, the carbonaceous material containing the iron-carbon composite (IV) used in the present invention is observed in a range of 200 to 2000 nm square by a transmission electron microscope, the length of the image is W, and the image is linearly formed. When the length when stretched is Wo, the shape characteristic means that the ratio W / Wo is 0.8 or more, particularly 0.9 or more.
- the iron-carbon composite (IV) that can be used in the present invention has the following properties when viewed as a bulk material. That is, in the present invention, iron is contained in the range of 10 to 90% of the space in the tube of the carbon tube selected from the nano flake carbon tube (a-1) and the multi-walled carbon nanotube (a-2) having the nested structure as described above.
- the iron-carbon composite (IV) filled with iron carbide (b) is not a trace amount that can be barely observed by microscopic observation, but is a bulk material containing a large number of the iron-carbon composite (IV). Thus, it is obtained in a large amount in the form of a carbonaceous material containing an iron-carbon composite (IV), or a material that should be called iron carbide or an iron-containing carbonaceous material.
- a carbonaceous material that can be used in the present invention comprising the nanoflake carbon tube (a-1) produced in Example 1 of JP-A-2002-338220 and iron carbide (b) filled in the space in the tube.
- An electron micrograph is shown in FIG.
- the carbonaceous material containing the iron-carbon composite (IV) used in the present invention basically, in almost all (particularly 99% or more) carbon tubes, the space 10 to 90% of the portion (that is, the space surrounded by the tube wall of the carbon tube) is filled with iron carbide or iron (b), and there is virtually no carbon tube with no space filled. It is normal. However, in some cases, a small amount of carbon tubes not filled with iron carbide or iron (b) may be present.
- the iron-carbon composite (IV) in which iron or iron carbide (b) is filled in 10 to 90% of the space in the carbon tube as described above is mainly used.
- soot may be contained in addition to the iron-carbonaceous composite (IV) that can be used in the present invention.
- the components other than the iron-carbonaceous composite that can be used in the present invention are removed, and the purity of the iron-carbonaceous composite (IV) in the carbonaceous material of the present invention is improved, so that the purity is substantially increased.
- a carbonaceous material consisting only of the iron-carbon composite (IV) used in the present invention can also be obtained.
- the carbonaceous material containing the iron-carbon composite (IV) used in the present invention can be synthesized in large quantities, and its weight can be easily increased. It can be 1 mg or more.
- the carbonaceous material that can be used in the present invention is iron or iron carbide (b) contained in powder X-ray diffraction measurement in which X-rays of CuK ⁇ are irradiated with an irradiation area of 25 mm 2 or more with respect to 1 mg of the carbonaceous material. ),
- the integrated intensity of the peak showing the strongest integrated intensity among the peaks of 40 ° ⁇ 2 ⁇ ⁇ 50 ° attributed to) is defined as Ia, and 26 is attributed to the average distance (d 002 ) between the carbon network surfaces of the carbon tubes.
- the ratio of Ia / Ib is referred to as an R value.
- This R value is the average of the entire carbonaceous material when the carbonaceous material containing the iron-carbon composite (IV) that can be used in the present invention is observed in an X-ray diffraction method with an X-ray irradiation area of 25 mm 2 or more. Since the peak intensity is observed as a value, it is not the inclusion rate or packing rate in one iron-carbon composite (IV) that can be measured by TEM analysis, but carbon that is an aggregate of iron-carbon composite (IV). The average value of the filling rate or inclusion rate of iron carbide or iron (b) as a whole material is shown.
- the average filling rate of the entire carbonaceous material including the iron-carbon composite (IV) that can be used in the present invention is determined by observing a plurality of fields of view with a TEM and a plurality of iron-carbons observed in each field of view. It can also be obtained by measuring the average filling rate of iron carbide or iron (b) in the composite (IV), and further calculating the average value of the average filling rates of a plurality of visual fields.
- the average filling rate of iron carbide or iron (b) as a whole carbonaceous material comprising the iron-carbon composite (IV) used in the present invention is about 10 to 90%, particularly 40 to About 70%.
- Nano flake carbon tube By iron-treating the iron-carbon composite (IV) in which the iron or iron carbide (b) is partially encapsulated in the inner space of the nanoflake carbon tube (a-1), Iron carbide (b) is dissolved and removed, and a hollow nanoflake carbon tube (III) in which iron or iron carbide (b) is not present in the space in the tube can be obtained.
- Examples of the acid used for the acid treatment include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and the like, and the concentration is preferably about 0.1 to 2N.
- an acid treatment method various methods can be used. For example, 1 g of iron-encapsulated nanoflake carbon tube is dispersed in 100 ml of 1N hydrochloric acid, and stirred at room temperature for 6 hours, followed by filtration and separation. Thereafter, the same treatment is performed twice with 100 ml of 1N hydrochloric acid to obtain a hollow nanoflake carbon tube (III).
- the length of the carbon network surface constituting the outermost surface is 500 nm or less, particularly 2 ⁇ 500 nm, especially 10 ⁇ 100 nm.
- Titanium oxide-coated nanoscale carbon has a titanium oxide coverage of 70-100% on the surface of the rod-like or fiber-like nanoscale carbon from the viewpoint of preventing leakage current. In particular, it is preferably 85 to 100%.
- the surface element ratio of carbon / titanium is preferably 0/100 to 70/30 (atomic ratio), more preferably 0/100 to 50/50 (atomic ratio).
- the surface coverage (ratio of the portion covered with the coating layer formed by continuous particulate titanium oxide on the surface of the carbon) can be determined by, for example, observation with an electron microscope (SEM or TEM) or the carbon /
- the surface element ratio of titanium can be measured by, for example, X-ray photoelectron spectroscopy.
- the nanoscale carbon existing in the titanium oxide-coated nanoscale carbon obtained in the step (A) is eliminated to produce a titanium oxide structure (1).
- the titanium oxide has an anatase type crystal structure and adhesion is increased.
- the nanoscale carbon may be eliminated, and the method is not particularly limited, but it is easy to eliminate the oxidation.
- the heating temperature is preferably 450 ° C. or higher, more preferably 550 ° C. or higher, further preferably 600 to 750 ° C., particularly preferably 600 to 700 ° C. .
- Porous titanium oxide composition The porous titanium oxide composition of the present invention comprises: (1) (1a) A rod-like, tubular or fibrous titanium oxide structure formed by continuous particulate titanium oxide, and (2) a mixture of particulate titanium oxide.
- Titanium oxide structure (1) The titanium oxide structure (1) is a rod-like, tubular, or fibrous structure in which particulate titanium oxide (1a) is continuous. This is the same as described in.
- particulate titanium oxide (2) As particulate titanium oxide (2), the same thing as particulate titanium oxide (1a) used for preparation of titanium oxide structure (1) may be used, and a different thing may be used. Specifically, the following can be used.
- the crystal structure of the particulate titanium oxide (2) is not particularly limited, but preferably includes at least one selected from the group consisting of anatase type titanium oxide, rutile type titanium oxide and brookite type titanium oxide. From the viewpoint of high light activity, those containing anatase-type titanium oxide are more preferable.
- the crystal structure of the particulate titanium oxide (2) can be measured by, for example, an X-ray diffraction method or Raman spectroscopic analysis.
- the average particle diameter of the particulate titanium oxide (2) is preferably 1 to 500 nm, more preferably 5 to 100 nm, from the viewpoint that more dye can be adsorbed and light can be absorbed.
- titanium oxide particles having a large particle size and large light scattering may be used in combination. Note that.
- the average particle diameter can be measured, for example, by observation with an electron microscope (SEM or TEM).
- Porous titanium oxide composition The porous titanium oxide composition of the present invention is obtained by mixing the titanium oxide structure (1) and the particulate titanium oxide (2).
- the titanium oxide structure (1) is not used alone but mixed with the particulate titanium oxide (2) to increase the fine irregularities on the surface as shown in FIG.
- the dye can be easily supported.
- the titanium oxide structure (1) is added in an amount of 0.1 to 90% by weight (more preferably 0.2 to 80% by weight (particularly 0.5%), from the viewpoint of ensuring fluidity during dispersion.
- particulate titanium oxide (2) is preferably mixed in an amount of 10 to 99.9 wt% (more preferably 20 to 99.8 wt% (especially 40 to 99.5 wt%)). If the content of the titanium oxide-coated carbon material (1) is 60% by weight or less, the coating property of the composition is high and the strength of the coating film is excellent, so that there is little variation and stable conductivity and photoelectric conversion efficiency. There is an advantage that it can be obtained. In addition, there is an advantage that higher photoelectric conversion efficiency can be obtained and the cost is low.
- the pores having a pore diameter of 5 to 50 nm are 40 to 100% of the total pores. In particular, it is preferably 60 to 100%.
- the specific surface area of the porous titanium oxide composition of the present invention is preferably from 30 to 500 m 2 / g, from the viewpoint of increasing the surface area, carrying a large amount of dye, and efficiently absorbing incident light.
- 500 m 2 / g is more preferable, and 60 to 500 m 2 / g is more preferable.
- titanium oxide particles having a large light scattering, that is, a small specific surface area may be used in combination.
- the porous titanium oxide composition of the present invention is, for example, (A1) A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex to produce a titanium oxide-coated nanoscale carbon.
- Process, (B1) The step of producing the titanium oxide structure (1) by eliminating the nanoscale carbon existing in the titanium oxide-coated nanoscale carbon obtained in the step (A1), and the step (C1) obtained in the step (B1). It is obtained by a method including a step of mixing the obtained titanium oxide structure (1) and particulate titanium oxide (2).
- Step (A1) Step (A1) in the method (1) for producing the porous titanium oxide composition is the same as step (A) in the method for producing the titanium oxide structure (1). That is, the nanoscale carbon, titanium fluoro complex, particulate titanium oxide (1a), conditions, etc. used in the step (A1) are the same as those in the step (A).
- Step (B1) in the method (1) for producing the porous titanium oxide composition is the same as step (B) in the method for producing the titanium oxide structure (1). That is, the disappearance method of nanoscale carbon, the heating temperature in the case of oxidative disappearance, and the like are the same as in step (B).
- Step (C1) In the step (C1), the titanium oxide structure (1) obtained in the step (B1) and the particulate titanium oxide (2) are mixed.
- the mixing method is not particularly limited, and examples thereof include known mixing methods such as paint shakers and mortars, various ball mills, sand mills, jet mills, kneaders, and rollers. It may be diluted with a solvent having a low viscosity, mixed with a paint shaker or the like, and then the solvent may be removed by distillation under reduced pressure or the like.
- porous titanium oxide composition of the present invention is not limited to the above production method (1), (A2) A coating layer in which particulate titanium oxide (1a) is continuous is formed on the surface of a rod-like or fibrous nanoscale carbon by a precipitation reaction from a titanium fluoro complex to produce a titanium oxide-coated nanoscale carbon. Process, (B2) The step of mixing the titanium oxide-coated nanoscale carbon obtained in the step (A2) and the particulate titanium oxide (2), and the (C2) titanium oxide-coated nanoparticle in the mixture obtained in the step (B2). It can also be produced by a method including a step of eliminating nanoscale carbon present in scale carbon.
- This production method (2) of the porous titanium oxide composition is obtained by reversing the order of the step (B1) and the step (C1) in the production method (1) of the porous titanium oxide composition.
- Step (A2) The step (A2) in the method (2) for producing the porous titanium oxide composition includes the step (A) in the method for producing the titanium oxide structure (1) and the step in the method (1) for producing the porous titanium oxide composition. Same as (A1). That is, the nanoscale carbon, titanium fluoro complex, particulate titanium oxide (1a) and conditions used in the step (A2) are the same as those in the step (A) and the step (A1).
- Step (B2) in the method (2) for producing the porous titanium oxide composition corresponds to step (C1) in the method (1) for producing the porous titanium oxide composition. That is, the particulate titanium oxide (2) and the mixing method used in the step (B2) are the same as those in the step (C1).
- Step (C2) Step (C2) in the method (2) for producing the porous titanium oxide composition includes step (B) in the method for producing the titanium oxide structure (1) and step in the method (1) for producing the porous titanium oxide composition. This corresponds to (B1). That is, the temperature conditions and the like in the step (C2) are the same as those in the step (B1).
- Photoelectric conversion element The photoelectric conversion element of the present invention comprises at least a conductive substrate, a semiconductor layer, a charge transport layer, and a counter electrode.
- the conductive substrate usually has an electrode layer on the substrate.
- the substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose.
- metal, colorless or colored glass, meshed glass, glass block, etc. are used.
- Colorless or colored resin may be used.
- resins include polyesters such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate, and polymethylpentene.
- substrate in this invention has a smooth surface at normal temperature, The surface may be a plane or a curved surface, and may deform
- the material of the conductive film that acts as an electrode is not particularly limited, and examples thereof include a metal such as gold, silver, chromium, copper, tungsten, and titanium, a metal thin film, and a conductive film made of a metal oxide.
- a metal oxide for example, Indium Tin Oxide (ITO (In 2 O 3 : Sn)), or Fluorine doped Tin Oxide (FTO (SnO 2 )) obtained by doping a metal oxide such as tin or zinc with a small amount of another metal element. : F)), Aluminum doped Zinc Oxide (AZO (ZnO: Al)), Antimony doped Tin Oxide (ATO (SnO 2 : Sb)), and the like are preferably used.
- the film thickness of the conductive film is usually 100 to 10,000 nm, preferably 500 to 3000 nm.
- the surface resistance (resistivity) is appropriately selected, but is usually 0.5 to 500 ⁇ / sq, preferably 1 to 50 ⁇ / sq.
- the formation method of the conductive film is not particularly limited, and a known method can be appropriately employed depending on the type of metal or metal oxide used. Usually, a vacuum deposition method, an ion plating method, a CVD method, a sputtering method, or the like is used. In either case, it is desirable that the substrate temperature be in the range of 20 to 700 ° C.
- the counter electrode (counter electrode) in the photoelectric conversion element of the present invention may have a single layer structure made of a conductive material, or may be composed of a conductive layer and a substrate.
- the substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose. For example, metal, colorless or colored glass, meshed glass, glass block, etc. are used. Resin may be used.
- the counter electrode may be formed by applying, plating, or vapor-depositing (PVD, CVD) a conductive material directly on the charge transport layer.
- PVD vapor-depositing
- the conductive material metals such as platinum, gold, nickel, titanium, aluminum, copper, silver and tungsten, and materials having a small specific resistance such as carbon materials and conductive organic substances are used.
- a metal lead may be used for the purpose of reducing the resistance of the counter electrode.
- the metal lead is preferably made of a metal such as platinum, gold, nickel, titanium, aluminum, copper, silver or tungsten, and particularly preferably made of aluminum or silver.
- the semiconductor layer a layer made of the above-described titanium oxide structure or porous titanium oxide composition of the present invention is used.
- the orientation direction of the titanium oxide structure of the present invention is not particularly limited, and the longitudinal direction does not necessarily have to be oriented in a specific direction such as substantially perpendicular to the substrate.
- the method for forming the semiconductor layer on the conductive substrate is not particularly limited.
- a paste containing the titanium oxide structure or porous titanium oxide composition of the present invention is prepared and applied on the conductive substrate.
- the method of baking etc. are mentioned.
- water, an organic solvent, or the like can be used as a solvent for the paste.
- the organic solvent is not particularly limited as long as it can disperse the titanium oxide structure or porous titanium oxide composition of the present invention.
- alcohols such as ethanol, methanol and terpineol
- glycols such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol can be used. These solvents are usually mixed and used in consideration of dispersibility, volatility, and viscosity.
- the proportion of the solvent in the paste is 50 to 90% by weight, particularly 70 to 85% in terms of providing fluidity during coating, maintaining the thickness after coating, and forming porous titanium oxide. % By weight is preferred.
- a thickener or the like may be included in addition to the above solvent.
- the thickener examples include alkyl celluloses such as methyl cellulose and ethyl cellulose. Among these, alkyl cellulose, particularly ethyl cellulose can be preferably used.
- the proportion of the thickener in the paste is preferably 2 to 20% by weight, particularly 3 to 15% by weight, from the viewpoint of balancing the fluidity during coating and the thickness after coating.
- the ratio of the solid content in the paste is preferably 10 to 50% by weight, and particularly preferably 15 to 30% by weight from the viewpoint of the balance between the fluidity at the time of application and the thickness after application, as described above.
- the titanium oxide structure (1) is preferably contained in an amount of 0.1 to 90% by weight (more preferably 0.2 to 80% by weight (particularly 0.5 to 60% by weight)) based on the solid content.
- a semiconductor layer with a dye supported is used for the purpose of improving the light absorption efficiency of the semiconductor layer.
- the dye is not particularly limited as long as it has absorption characteristics in the visible region and near infrared region, and improves (sensitizes) the light absorption efficiency of the semiconductor layer.
- metal complex dyes, organic dyes, natural dyes, semiconductors, etc. Is preferred.
- a functional group such as a carboxyl group, a hydroxyl group, a sulfonyl group, a phosphonyl group, a carboxylalkyl group, a hydroxyalkyl group, a sulfonylalkyl group, a phosphonylalkyl group, etc. Those having a group are preferably used.
- metal complex dye for example, a ruthenium, osmium, iron, cobalt, zinc, mercury complex (for example, mellicle chromium), metal phthalocyanine, chlorophyll, or the like can be used.
- organic dyes include, but are not limited to, cyanine dyes, hemicyanine dyes, merocyanine dyes, xanthene dyes, triphenylmethane dyes, metal-free phthalocyanine dyes, and the like.
- an amorphous semiconductor having a large i-type light absorption coefficient, a direct transition semiconductor, or a fine particle semiconductor that exhibits a quantum size effect and efficiently absorbs visible light is preferable.
- one of various semiconductors, metal complex dyes and organic dyes, or two or more kinds of dyes can be mixed in order to make the wavelength range of photoelectric conversion as wide as possible and increase the conversion efficiency.
- dye to mix and its ratio can be selected so that it may match with the wavelength range and intensity distribution of the target light source.
- a solution in which the dye is dissolved in a solvent is applied on the semiconductor layer by spray coating, spin coating, or the like and then dried.
- the substrate may be heated to an appropriate temperature.
- a method in which the semiconductor layer is immersed in a solution and adsorbed can be used.
- the immersion time is not particularly limited as long as the dye is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, more preferably 1 to 20 hours.
- the concentration of the dye in the case of the solution is about 1 to 1000 mmol / L, preferably about 10 to 500 mmol / L.
- the solvent to be used is not particularly limited, but water and organic solvents are preferably used.
- the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol; acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, and the like.
- Nitriles aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, and p-xylene; aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; acetone, methyl ethyl ketone Ketones such as diethyl ketone and 2-butanone; ethers such as diethyl ether and tetrahydrofuran; ethylene carbonate, propylene carbonate, nitromethane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, dimethoxy Ethane, ⁇ -butyrolactone, ⁇ -valerolactone, sulfolane, dimethoxyethane, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide
- a colorless compound having a property as a surfactant may be added to the dye adsorbing solution and co-adsorbed on the semiconductor layer.
- colorless compounds include steroid compounds such as cholic acid having a carboxyl group or sulfo group, deoxycholic acid, chenodeoxycholic acid, taurodeoxycholic acid, sulfonates, and the like.
- the unadsorbed dye is preferably removed by washing immediately after the adsorption step. Washing is preferably performed using acetonitrile, an alcohol solvent or the like in a wet washing tank.
- the surface of the layer may be treated.
- preferred amines include pyridine, 4-t-butylpyridine, polyvinylpyridine and the like.
- preferred quaternary ammonium salts include tetrabutylammonium iodide, tetrahexylammonium iodide, and the like. These may be used by dissolving in an organic solvent, or may be used as they are in the case of a liquid.
- the charge transport layer contains a charge transport material having a function of replenishing electrons to the oxidant of the dye.
- the charge transport material used in the present invention is a charge transport material in which ions are involved.
- the electrolyte solution as a charge transport material involving ions is preferably composed of an electrolyte, a solvent, and an additive.
- electrolyte used in the electrolytic solution iodine and iodide (LiI, NaI, KI, CsI, metal iodide such as CaI 2, tetraalkylammonium iodide, pyridinium iodide, quaternary ammonium such as imidazolium iodide
- iodine and iodide LiI, NaI, KI, CsI, metal iodide such as CaI 2, tetraalkylammonium iodide, pyridinium iodide, quaternary ammonium such as imidazolium iodide
- bromine and bromide metal bromide such as LiBr, NaBr, KBr, CsBr, CaBr, CaBr 2 ,
- an electrolyte obtained by combining I 2 and LiI or a quaternary ammonium compound iodine salt such as pyridinium iodide or imidazolium iodide is preferable.
- the electrolyte may be used as a mixture.
- Any solvent can be used as long as it is generally used in electrochemical cells and batteries.
- the room temperature molten salt is a salt composed of an ion pair that is melted at room temperature (that is, in a liquid state) and usually has a melting point of 20 ° C. or lower and is a liquid at a temperature exceeding 20 ° C. Is a salt.
- the solvent may be used alone or in combination of two or more.
- a basic compound such as 4-t-butylpyridine, 2-picoline, 2,6-lutidine
- a preferable concentration range when adding the basic compound to the electrolytic solution is 0.05 to 2 mol / L.
- the basic compound When added to the molten salt electrolyte composition, the basic compound preferably has an ionic group.
- the blending ratio of the basic compound with respect to the entire molten salt electrolyte composition is preferably 1 to 40% by mass, more preferably 5 to 30% by mass.
- a material that can be used as a polymer matrix there is no particular limitation as long as a solid state or a gel state is formed by a polymer matrix alone or by adding a plasticizer, a supporting electrolyte, or a plasticizer and a supporting electrolyte. Commonly used so-called polymer compounds can be used.
- Examples of the polymer compound exhibiting characteristics as the polymer matrix include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and methyl acrylate. And polymer compounds obtained by polymerizing or copolymerizing monomers such as ethyl acrylate, methyl methacrylate, styrene, and vinylidene fluoride. These polymer compounds may be used alone or in combination. Among these, a polyvinylidene fluoride polymer compound is particularly preferable.
- the charge transport layer can be formed by one of two methods.
- the first method is a method in which a semiconductor layer and a counter electrode are bonded together, and a liquid charge transport layer is sandwiched between the gaps.
- the second method is a method in which a charge transport layer is provided directly on the semiconductor layer, and a counter electrode is provided thereafter.
- a counter electrode is usually applied in an undried state to take measures to prevent liquid leakage at the edge.
- Comparative Example 1 A powder obtained by firing titanium oxide particles having a particle diameter of 20 nm for 1 hour at 650 ° C. was processed into a flat plate having a thickness of 0.3 mm at a pressure of 10 MPa, and a current value of 0.065 ⁇ A flowing when a voltage of 1 V was applied between the pellets. It was. From this, it can be seen that the powder resistance is 3.8 ⁇ 10 6 ⁇ ⁇ m.
- Example 1 To 0.96 g of nanoscale carbon tube (average diameter: 35 nm, average length: 5 ⁇ m, average aspect ratio: 143), 69 g of nitric acid 150 g was added and held at 90 to 95 ° C. for 6 hours. This was filtered, washed with distilled water until the filtrate reached pH 6-7, and then dried.
- nanoscale carbon dispersion liquid ammonium hexafluorotitanate diluted to 1.0 M and boric acid diluted to 1.0 M were added so that the respective concentrations would be 0.20 M and 0.4 M. After standing for a period of time, it was filtered and dried to obtain a structure (titanium oxide-coated nanoscale carbon tube) in which the surface of the nanoscale carbon tube was coated with titanium oxide.
- X-ray photoelectron spectroscopy does not expose the nanoscale carbon tube because it is an analysis of a few nanometer parts of the surface, It can be seen that titanium oxide is coated.
- This titanium oxide-coated nanoscale carbon tube was baked in air at 600 ° C. for 1 hour to eliminate the nanoscale carbon tube, thereby obtaining a tubular titanium oxide structure in which particulate titanium oxide was continuous.
- the anatase type was mainly used.
- the tube had an average diameter of 80 to 150 nm, an average length of about 1000 to 10,000 nm, and an average aspect ratio of about 10 to 100.
- Electron beam diffraction measurement was performed at points A to C in FIG. 9 (end portion of the titanium oxide structure) and D to F in FIG. 10 (center portion of the titanium oxide structure). The following structure was confirmed.
- Example 1 The structure produced in Example 1 was processed into a flat plate with a thickness of 0.3 mm at a pressure of 10 MPa, and when a voltage of 1 V was applied between the pellets, a current of 0.1 ⁇ A was observed and the same method was used. It confirmed that it showed high electroconductivity compared with the comparative example 1 using the evaluated titanium oxide particle. From this, it can be seen that the powder resistance is 1.9 ⁇ 10 6 ⁇ ⁇ m.
- Example 2 To 0.48 g of nanoscale carbon tube (average diameter: 10 nm, average length: 10 ⁇ m, average aspect ratio: 1000), 150 g of 69% nitric acid was added and held at 90 to 95 ° C. for 3 hours. This was filtered, washed with distilled water until the filtrate reached pH 6-7, and then dried.
- This titanium oxide-coated nanoscale carbon tube was baked in air at 600 ° C. for 1 hour to eliminate the nanoscale carbon tube, thereby obtaining a tubular titanium oxide structure in which particulate titanium oxide was continuous.
- the anatase type was mainly used.
- titanium oxide fine particles of 2 to 15 nm gathered to have a thickness of about 10 to 30 nm, an average diameter of 30 to 70 nm, and an average length of 3000 to 10000 nm. It was a tube having an average aspect ratio of about 50 to 300.
- Example 3 To 0.96 g of nanoscale carbon tube (average diameter: 100 nm, average length: 10 ⁇ m, average aspect ratio: 100), 150 g of 69% nitric acid was added and held at 90-95 ° C. for 6 hours. This was filtered, washed with distilled water until the filtrate reached pH 6-7, and then dried.
- nanoscale carbon dispersion liquid ammonium hexafluorotitanate diluted to 1.0 M and boric acid diluted to 1.0 M were added so that the respective concentrations would be 0.2 M and 0.4 M. After standing for a period of time, it was filtered and dried to obtain a structure (titanium oxide-coated nanoscale carbon tube) in which the surface of the nanoscale carbon tube was coated with titanium oxide.
- the titanium oxide-coated nanoscale carbon tube was baked in air at 700 ° C. for 2 hours to eliminate the nanoscale carbon tube, thereby obtaining a tubular titanium oxide structure in which particulate titanium oxide was continuous.
- the anatase type was mainly used.
- Example 4 Only the firing temperature of Example 1 was changed to 750 ° C., and a titanium oxide structure was obtained in the same manner as in Example 1 except that.
- Example 4 The structure produced in Example 4 was processed into a flat plate with a thickness of 0.3 mm at a pressure of 10 MPa in the same manner as in Example 1, and when a voltage of 1 V was applied between the pellets, a current of 0.242 ⁇ A was observed to flow. And it confirmed that the electroconductivity showed high electroconductivity compared with the comparative example 1 using the titanium oxide particle evaluated by the same method. From this, it is understood that the powder resistance is 1.08 ⁇ 10 6 ⁇ ⁇ m.
- Example 5 Only the firing atmosphere of Example 4 was changed to nitrogen, and a titanium oxide structure was obtained in the same manner as in Example 4 (the firing temperature was 750 ° C.) except that.
- Example 5 The structure (titanium oxide-coated nanoscale carbon tube) produced in Example 5 was processed into a flat plate with a thickness of 0.3 mm at a pressure of 10 MPa in the same manner as in Example 4, and a voltage of 1 V was applied between the pellets. It was observed that a current of .3 ⁇ A flows, and it was confirmed that it showed higher conductivity than Comparative Example 1 using titanium oxide particles evaluated by the same method. From this, it can be seen that the powder resistance is 4.96 ⁇ 10 4 ⁇ ⁇ m.
- Examples 6 to 11 and Comparative Example 1 Weight ratios shown in Table 1 for the titanium oxide structure produced in Production Example 1 and particulate titanium oxide (crystal structure: anatase type) having an average particle diameter of 18 nm (manufactured by Catalyst Kasei Kogyo Co., Ltd .: HPW-18NR) Comparative Example 1 was mixed with particulate titanium oxide alone, and Comparative Example 2 was mixed with titanium oxide structure alone. To 20 parts by weight of the obtained mixture, 10 parts by weight of ethyl cellulose and 70 parts by weight of ⁇ -terpineol were added and kneaded with a three-roll to prepare a paste.
- This paste was applied to a glass substrate with a transparent electrode by a screen printer and baked at 500 ° C. for 1 hour to produce an electrode film having a thickness of 12 ⁇ m.
- a platinum-plated counter electrode was bonded to a glass substrate with a transparent electrode through a spacer, and an electrolyte solution of 0.6 mol / l lithium iodide in anhydrous acetonitrile and 0.06 mol / l iodine was used as an electrolyte.
- An anhydrous acetonitrile solution was injected to produce a photoelectric conversion element.
- Examples 6 to 11 using the titanium oxide structure of the present invention a higher photoelectric conversion efficiency was obtained than in Comparative Example 1. Further, in Examples 6 to 10 using the porous titanium oxide composition of the present invention, higher photoelectric conversion characteristics were obtained as compared with Example 11 of the titanium oxide structure alone of the present invention. In Examples 6 to 10, it can be seen that Examples 6 to 10 are more excellent than Example 11 because the coating property of the composition and the strength of the coating film are excellent and the cost can be kept low. It was.
- Example 9 In Comparative Example 1, the diffusion of ions in the electrolytic solution was suppressed, whereas in Example 9 having an appropriate pore distribution, the diffusion of ions became smooth and became a factor in improving the photoelectric conversion efficiency. Conceivable.
- Example 11 when the pore distribution of the electrode film obtained in Example 11 was measured in the same manner, it was distributed mainly at 20 to 100 nm centering on 80 nm (5 to 50 nm pores: 13%).
- Example 9 shows that both the conductivity and the diffusion of ions in the electrolyte can be achieved in comparison with Example 11.
- SYMBOLS 100 TEM image of nano flake carbon tube in longitudinal direction 110 Graph image of substantially straight graphene sheet 200 TEM image of cross section almost perpendicular to longitudinal direction of nano flake carbon tube 210 Arc shape graphene sheet image 300 Longitudinal direction of nested multi-layer carbon nanotube 400 A straight line graphene sheet image continuous over its entire length 400 A TEM image of a cross section perpendicular to the longitudinal direction of a nested multi-walled carbon nanotube
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Abstract
Description
(B)酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程
を含む項1~10のいずれかに記載の酸化チタン構造体の製造方法。
(2)粒子状酸化チタン
を混合してなる多孔質酸化チタン組成物。
(B1)工程(A1)で得られた酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させ、酸化チタン構造体(1)を作製する工程、及び
(C1)工程(B1)で得られた酸化チタン構造体(1)と粒子状酸化チタン(2)とを混合する工程
を含む項16~21のいずれかに記載の多孔質酸化チタン組成物の製造方法。
(B2)工程(A2)で得られた酸化チタン被覆ナノスケールカーボンと粒子状酸化チタン(2)とを混合する工程、及び
(C2)工程(B2)で得られた混合物中の酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程
を含む項16~21のいずれかに記載の多孔質酸化チタン組成物の製造方法。
本発明の棒状、管状又は繊維状の酸化チタン構造体(1)は、粒子状酸化チタン(1a)が連なってなる。本発明の酸化チタン構造体(1)としては、棒状、管状、繊維状のもののなかでも、表面積が大きい点から、管状のものが好ましい。また、本発明では、連なってなるとは、微粒子状酸化チタン(1a)が、隣接する酸化チタン(1a)と密接に接しており、ただ単に混合して得られる状態のものではない。
粒子状酸化チタン(1a)の結晶構造としては、とくに制限されるわけではないが、アナターゼ型酸化チタン、ルチル型酸化チタン及びブルッカイト型酸化チタンよりなる群から選ばれる少なくとも1種を含むものが好ましく、光に対する活性が高い点から、アナターゼ型酸化チタンを含むものがより好ましい。なお、粒子状酸化チタン(1a)の結晶構造は、例えば、X線回折法、ラマン分光分析等により測定することができる。また、粒子状酸化チタン(1a)としては、アナターゼ型酸化チタン、ルチル型酸化チタン及びブルッカイト型酸化チタンに加えて、さらに、2価チタンの酸化物及び3価チタンの酸化物よりなる群から選ばれる少なくとも1種を含むことが好ましい。
本発明の酸化チタン構造体(1)は、色素を多量に担持し、入射した光を効率よく吸収する点から、比表面積が20m2/g以上であるものが好ましく、比表面積が70m2/g以上であるものがより好ましく、80m2/g以上であるものがさらに好ましい。比表面積は、大きいほうが好ましく、上限値は特に制限されないが、3000m2/g程度である。なお、比表面積は、BET法等により測定できる。
本発明の酸化チタン構造体(1)は、
(A)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B)酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程により得られる。
工程(A)では、棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する。
本発明で使用する棒状又は繊維状のナノスケールカーボンとしては、特に制限はないが、ナノスケールカーボンチューブを使用することが好ましい。このナノスケールカーボンチューブは、導電性を有する物質で形成されているのが好ましい。
本発明で使用できるナノスケールカーボンチューブとしては、ナノサイズの直径を有するカーボンチューブを指し、該カーボンチューブのチューブ内空間部には鉄等が内包されていてもよい。
(I)単層カーボンナノチューブ又は多層カーボンナノチューブ、
(II)本出願人が開発したアモルファスナノスケールカーボンチューブ、
(III)ナノフレークカーボンチューブ、
(IV)(a)ナノフレークカーボンチューブ及び入れ子構造の多層カーボンナノチューブよりなる群から選ばれるカーボンチューブと(b)炭化鉄又は鉄とからなり、該カーボンチューブ(a)のチューブ内空間部の10~90%の範囲に(b)の炭化鉄又は鉄が充填されている鉄-炭素複合体、
(V)これらの2種以上の混合物
等を例示することができる。
カーボンナノチューブ(I)は、黒鉛シート(即ち、黒鉛構造の炭素原子面ないしグラフェンシート)がチューブ状に閉じた中空炭素物質であり、その直径はナノメートルスケールであり、壁構造は黒鉛構造を有している。カーボンナノチューブ(I)のうち、壁構造が一枚の黒鉛シートでチューブ状に閉じたものは単層カーボンナノチューブと呼ばれ、複数枚の黒鉛シートがそれぞれチューブ状に閉じて、入れ子状になっているものは入れ子構造の多層カーボンナノチューブと呼ばれている。本発明では、これら単層カーボンナノチューブ及び入れ子構造の多層カーボンナノチューブがいずれも使用できる。
また、アモルファスナノスケールカーボンチューブ(II)は、WO00/40509(日本国特許第3355442号)に記載されており、カーボンからなる主骨格を有し、直径が0.1~1000nmであり、アモルファス構造を有するナノスケールカーボンチューブであって、直線状の形態を有し、X線回折法(入射X線:CuKα)において、ディフラクトメーター法により測定される炭素網平面(002)の平面間隔(d002)が3.54Å以上、特に3.7Å以上であり、回折角度(2θ)が25.1度以下、特に24.1度以下であり、2θバンドの半値幅が3.2度以上、特に7.0度以上であることを特徴とするものである。
また、本発明で使用できる鉄-炭素複合体(IV)は、特開2002-338220号公報(特許第3569806号)に記載されており、(a)ナノフレークカーボンチューブ及び入れ子構造の多層カーボンナノチューブよりなる群から選ばれるカーボンチューブと(b)炭化鉄又は鉄とからなり、該カーボンチューブ(a)のチューブ内空間部の10~90%の範囲に(b)の炭化鉄又は鉄が充填されている。即ち、チューブ内空間部の100%の範囲に完全に充填されているものではなく、上記炭化鉄又は鉄がそのチューブ内空間部の10~90%の範囲に充填されている(即ち、部分的に充填されている)ことを特徴とするものである。壁部は、パッチワーク状ないし張り子状(いわゆるpaper mache状)のナノフレークカーボンチューブである。
(1)不活性ガス雰囲気中、圧力を10-5Pa~200kPaに調整し、反応炉内の酸素濃度を、反応炉容積をA(リットル)とし酸素量をB(Ncc)とした場合の比B/Aが1×10-10~1×10-1となる濃度に調整した反応炉内でハロゲン化鉄を600~900℃まで加熱する工程、及び
(2)上記反応炉内に不活性ガスを導入し、圧力10-5Pa~200kPaで熱分解性炭素源を導入して600~900℃で加熱処理を行う工程
を包含する製造方法により製造される。
本発明で使用できるナノフレークカーボンチューブ(a-1)と炭化鉄又は鉄(b)からなる鉄-炭素複合体(IV)は、典型的には円柱状であるが、そのような円柱状の鉄-炭素複合体(特開2002-338220号公報の実施例1で得られたもの)の長手方向にほぼ垂直な断面の透過型電子顕微鏡(TEM)写真を図6に示し、側面のTEM写真を図4に示す。
前記のように、工程(1)及び(2)を行った後、特定の加熱工程を行うことにより、得られる鉄-炭素複合体(IV)を構成するカーボンチューブは、入れ子構造の多層カーボンナノチューブ(a-2)となる。
本明細書において、上記ナノフレークカーボンチューブ(a-1)及び入れ子構造の多層カーボンナノチューブ(a-2)よりなる群から選ばれるカーボンチューブ内空間部の炭化鉄又は鉄(b)による充填率(10~90%)は、本発明で使用できる鉄-炭素複合体(IV)を透過型電子顕微鏡で観察し、各カーボンチューブの空間部(即ち、カーボンチューブのチューブ壁で囲まれた空間)の像の面積に対する、炭化鉄又は鉄(b)が充填されている部分の像の面積の割合である。
本発明で使用できる鉄-炭素複合体(IV)は、湾曲が少なく、直線状であり、壁部の厚さが全長に亘ってほぼ一定の均一厚さを有しているので、全長に亘って均質な形状を有している。その形状は、柱状で、主に円柱状である。
上記の鉄又は炭化鉄(b)がナノフレークカーボンチューブ(a-1)のチューブ内空間に部分内包されている鉄-炭素複合体(IV)を酸処理することにより、内包されている鉄又は炭化鉄(b)が溶解除去され、チューブ内空間部に鉄又は炭化鉄(b)が存在しない中空のナノフレークカーボンチューブ(III)を得ることができる。
このようにして得られる酸化チタン被覆ナノスケールカーボンは、漏れ電流を防止する点から、棒状又は繊維状のナノスケールカーボンの表面の酸化チタンの被覆率が、70~100%、特には85~100%であることが好ましい。また、カーボン/チタンの表面元素比率は、0/100~70/30(原子比)が好ましく、0/100~50/50(原子比)がより好ましい。なお、表面被覆率(カーボンの表面上の、粒子状酸化チタンが連なってなる被覆層で覆われている箇所の割合)は、例えば、電子顕微鏡(SEM又はTEM)観察等により、また、カーボン/チタンの表面元素比率は、例えば、X線光電子分光分析等により、測定することができる。
工程(B)では、工程(A)で得られた酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させ、酸化チタン構造体(1)を作製する。これにより、酸化チタンがアナターゼ型結晶構造になるとともに密着性が増す利点がある。なお、工程(B)では、ナノスケールカーボンを消失させればよく、その手法は特に限定されるものではないが、酸化消失させるのが簡便である。例えば、空気中で加熱して酸化消失させる場合には、その加熱温度は、好ましくは450℃以上、より好ましくは550℃以上、さらに好ましくは600~750℃、特に好ましくは600~700℃である。
本発明の多孔質酸化チタン組成物は、
(1)(1a)粒子状酸化チタンが連なってなる棒状、管状又は繊維状の酸化チタン構造体、及び
(2)粒子状酸化チタン
を混合してなる。
酸化チタン構造体(1)は、粒子状酸化チタン(1a)が連なってなる棒状、管状又は繊維状のものであり、1.で説明したものと同じものである。
粒子状酸化チタン(2)としては、酸化チタン構造体(1)の作製に使用した粒子状酸化チタン(1a)と同じものを用いてもよいし、違うものを用いてもよい。具体的には、以下のものが使用できる。
本発明の多孔質酸化チタン組成物は、上記の酸化チタン構造体(1)及び粒子状酸化チタン(2)を混合してなる。
本発明の多孔質酸化チタン組成物は、例えば、
(A1)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B1)工程(A1)で得られた酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させ、酸化チタン構造体(1)を作製する工程、及び
(C1)工程(B1)で得られた酸化チタン構造体(1)と粒子状酸化チタン(2)とを混合する工程
を含む方法により得られる。
多孔質酸化チタン組成物の製造方法(1)における工程(A1)は、酸化チタン構造体(1)の製造方法における工程(A)と同じである。つまり、工程(A1)において使用するナノスケールカーボン、チタンフルオロ錯体、粒子状酸化チタン(1a)や条件等は工程(A)と同じである。
多孔質酸化チタン組成物の製造方法(1)における工程(B1)は、酸化チタン構造体(1)の製造方法における工程(B)と同じである。つまり、ナノスケールカーボンの消失方法、酸化消失させる場合の加熱温度等は工程(B)と同じである。
工程(C1)では、工程(B1)で得られた酸化チタン構造体(1)と粒子状酸化チタン(2)とを混合する。
本発明の多孔質酸化チタン組成物は、上記の製造方法(1)に限定されることはなく、
(A2)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B2)工程(A2)で得られた酸化チタン被覆ナノスケールカーボンと粒子状酸化チタン(2)とを混合する工程、及び
(C2)工程(B2)で得られた混合物中の酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程
を含む方法によっても製造することができる。
多孔質酸化チタン組成物の製造方法(2)における工程(A2)は、酸化チタン構造体(1)の製造方法における工程(A)、及び多孔質酸化チタン組成物の製造方法(1)における工程(A1)と同じである。つまり、工程(A2)において使用するナノスケールカーボン、チタンフルオロ錯体、粒子状酸化チタン(1a)や条件等は、工程(A)及び工程(A1)と同じである。
多孔質酸化チタン組成物の製造方法(2)における工程(B2)は、多孔質酸化チタン組成物の製造方法(1)における工程(C1)に対応するものである。つまり、工程(B2)における使用する粒子状酸化チタン(2)や混合手法等は、工程(C1)と同様である。
多孔質酸化チタン組成物の製造方法(2)における工程(C2)は、酸化チタン構造体(1)の製造方法における工程(B)、及び多孔質酸化チタン組成物の製造方法(1)における工程(B1)に対応するものである。つまり、工程(C2)における温度条件等は、工程(B1)と同様である。
本発明の光電変換素子は、導電性基板、半導体層、電荷輸送層及び対向電極から少なくとも構成される。
粒径20nmの酸化チタン粒子を650℃で1時間焼成した粉末を10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加して流れる電流値は0.065μAであった。このことから、粉体抵抗は、3.8×106Ω・mであることがわかる。
ナノスケールカーボンチューブ(平均直径:35nm、平均長さ:5μm、平均アスペクト比:143)0.96gに69%硝酸150gを加え、90~95℃にて6時間保持した。これをろ過し、蒸留水にてろ液がpH6~7になるまで洗浄した後、乾燥させた。
実施例1にて作製した構造体を10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加したところ0.1μAの電流が流れることを観測し、同様の方法で評価した酸化チタン粒子を用いた比較例1に比べて高い導電性を示すことを確認した。このことから、粉体抵抗は、1.9×106Ω・mであることがわかる。
ナノスケールカーボンチューブ(平均直径:10nm、平均長さ:10μm、平均アスペクト比:1000)0.48gに69%硝酸150gを加え、90~95℃にて3時間保持した。これをろ過し、蒸留水にてろ液がpH6~7になるまで洗浄した後、乾燥させた。
実施例2にて作製した構造体を10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加したところ粉体抵抗は、平均で1.50×106Ω・mであった。
ナノスケールカーボンチューブ(平均直径:100nm、平均長さ:10μm、平均アスペクト比:100)0.96gに69%硝酸150gを加え、90~95℃にて6時間保持した。これをろ過し、蒸留水にてろ液がpH6~7になるまで洗浄した後、乾燥させた。
実施例3にて作製した構造体を10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加したところ粉体抵抗は、平均で1.10×106Ω・mであった。
実施例1の焼成温度だけを750℃に変更し、それ以外は実施例1と同様の工程で酸化チタン構造体を得た。
実施例4にて作製した構造体を実施例1と同様に10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加したところ0.242μAの電流が流れることを観測し、同様の方法で評価した酸化チタン粒子を用いた比較例1に比べて高い導電性を示すことを確認した。このことから、粉体抵抗は、1.08×106Ω・mであることがわかる。
実施例4の焼成雰囲気だけを窒素に変更し、それ以外は実施例4と同様の工程で(焼成温度は750℃)酸化チタン構造体を得た。
実施例5にて作製した構造体(酸化チタン被覆ナノスケールカーボンチューブ)を実施例4と同様に10MPaの圧力で厚さ0.3mmの平板状に加工し、ペレット間に電圧1V印加したところ52.3μAの電流が流れることを観測し、同様の方法で評価した酸化チタン粒子を用いた比較例1に比べて高い導電性を示すことを確認した。このことから、粉体抵抗は、4.96×104Ω・mであることがわかる。
製造例1により作製した酸化チタン構造体と平均粒子径18nm(触媒化成工業(株)製:HPW-18NR)の粒子状酸化チタン(結晶構造:アナターゼ型)とをそれぞれ表1に示す重量比(比較例1は粒子状酸化チタン単独、比較例2は酸化チタン構造体単独)で混合した。得られた混合物20重量部にエチルセルロースを10重量部、α-テルピネオールを70重量部加え、三本ロールにて混錬し、ペーストを作製した。
作製した面積0.25cm2の光電変換素子に、山下電装(株)製のソーラーシミュレーターでAM1.5(JISC8912Aランク)の条件下の100mW/cm2の強度の光を照射して、光電変換特性を評価した。
比較例1で得られた電極膜の細孔分布を比表面積細孔分布測定装置により測定したところ、4nmを中心に、主に3~6nmの範囲に分布していた(5~50nmの細孔:12%)。
110 略直線状のグラフェンシート像
200 ナノフレークカーボンチューブの長手方向にほぼ垂直な断面のTEM像
210 弧状グラフェンシート像
300 入れ子構造の多層カーボンナノチューブの長手方向の全長にわたって連続する直線状グラフェンシート像
400 入れ子構造の多層カーボンナノチューブの長手方向に垂直な断面のTEM像
Claims (24)
- (1a)粒子状酸化チタンが連なってなる棒状、管状又は繊維状の酸化チタン構造体。
- 粒子状酸化チタン(1a)の平均粒子径が1~200nmである請求項1に記載の酸化チタン構造体。
- 長軸に直交する平均直径が5~500nm、長軸の平均長さが0.1~1000μmであり、平均アスペクト比が3~200000である請求項1又は2に記載の酸化チタン構造体。
- 10MPa圧力下での粉体抵抗が3×106Ω・m以下である請求項1~3のいずれかに記載の酸化チタン構造体。
- 管状である請求項1~4のいずれかに記載の酸化チタン構造体。
- 肉厚が2~500nmである請求項5に記載の酸化チタン構造体。
- 粒子状酸化チタン(1a)が、アナターゼ型酸化チタン、ルチル型酸化チタン及びブルッカイト型酸化チタンよりなる群から選ばれる少なくとも1種を含む請求項1~6のいずれかに記載の酸化チタン構造体。
- 粒子状酸化チタン(1a)が、アナターゼ型酸化チタン、ルチル型酸化チタン及びブルッカイト型酸化チタンよりなる群から選ばれる少なくとも1種に加えて、さらに、2価チタンの酸化物及び3価チタンの酸化物よりなる群から選ばれる少なくとも1種を含む請求項7に記載の酸化チタン構造体。
- 粒子状酸化チタン(1a)が、マグネリ相構造の結晶形態を有する酸化チタンを含む、請求項1~8のいずれかに記載の酸化チタン構造体。
- 比表面積が20m2/g以上である請求項1~9のいずれかに記載の酸化チタン構造体。
- (A)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B)酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程
を含む請求項1~10のいずれかに記載の酸化チタン構造体の製造方法。 - 酸化チタン被覆ナノスケールカーボンが、電子顕微鏡観察により測定される、ナノスケールカーボンの表面の酸化チタンの被覆率が、70~100%である請求項11に記載の酸化チタン構造体の製造方法。
- 酸化チタン被覆ナノスケールカーボンが、X線光電子分光分析によるカーボン/チタンの表面元素比率が0/100~70/30(原子比)である請求項11又は12に記載の酸化チタン構造体の製造方法。
- 棒状又は繊維状のナノスケールカーボンの長軸に直交する平均直径が1~100nm、長軸の平均長さが0.1~1000μmであり、平均アスペクト比が5~1000000である請求項11~13のいずれかに記載の酸化チタン構造体の製造方法。
- 棒状又は繊維状のナノスケールカーボンが、ナノスケールカーボンチューブである請求項11~14のいずれかに記載の酸化チタン構造体の製造方法。
- (1)請求項1~10のいずれかに記載の酸化チタン構造体、及び
(2)粒子状酸化チタン
を混合してなる多孔質酸化チタン組成物。 - 酸化チタン構造体(1)を0.1~90重量%、粒子状酸化チタン(2)を10~99.9重量%混合してなる請求項16に記載の多孔質酸化チタン組成物。
- 粒子状酸化チタン(2)の平均粒子径が1~500nmである請求項16又は17に記載の多孔質酸化チタン組成物。
- 粒子状酸化チタン(2)が、アナターゼ型酸化チタン、ルチル型酸化チタン及びブルッカイト型酸化チタンよりなる群から選ばれる少なくとも1種を含む請求項16~18のいずれかに記載の多孔質酸化チタン組成物。
- 比表面積が30m2/g以上である請求項16~19のいずれかに記載の多孔質酸化チタン組成物。
- 空孔径が5~50nmの空孔が、全空孔の40~100%存在する請求項16~20のいずれかに記載の多孔質酸化チタン組成物。
- (A1)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B1)工程(A1)で得られた酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させ、酸化チタン構造体(1)を作製する工程、及び
(C1)工程(B1)で得られた酸化チタン構造体(1)と粒子状酸化チタン(2)とを混合する工程
を含む請求項16~21のいずれかに記載の多孔質酸化チタン組成物の製造方法。 - (A2)棒状又は繊維状のナノスケールカーボンの表面に、チタンフルオロ錯体からの析出反応により、粒子状酸化チタン(1a)が連なってなる被覆層を形成し、酸化チタン被覆ナノスケールカーボンを作製する工程、
(B2)工程(A2)で得られた酸化チタン被覆ナノスケールカーボンと粒子状酸化チタン(2)とを混合する工程、及び
(C2)工程(B2)で得られた混合物中の酸化チタン被覆ナノスケールカーボン中に存在するナノスケールカーボンを消失させる工程
を含む請求項16~21のいずれかに記載の多孔質酸化チタン組成物の製造方法。 - 請求項1~10のいずれかに記載の酸化チタン構造体又は請求項16~21のいずれかに記載の多孔質酸化チタン組成物を含む活性物質の表面に色素を担持することを特徴とする光電変換素子。
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KR (1) | KR101332526B1 (ja) |
CN (1) | CN102066260A (ja) |
WO (1) | WO2009154274A1 (ja) |
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US20120312370A1 (en) * | 2011-06-07 | 2012-12-13 | Mcgill University | Hybrid dye-sensitized solar cell photoanodes based on aqueous synthesized titanium dioxide |
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KR20130081466A (ko) * | 2012-01-09 | 2013-07-17 | 삼성에스디아이 주식회사 | 염료감응 태양전지 |
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TWI481041B (zh) * | 2012-07-16 | 2015-04-11 | Nat Univ Chung Hsing | A method of manufacturing a photoelectrode having a high photoelectric conversion rate, and a dye-sensitized solar cell using the photoelectrode |
CN107428553B (zh) * | 2015-03-31 | 2020-09-29 | 日本贵弥功株式会社 | 钛氧化物粒子、钛氧化物粒子的制造方法、蓄电元件用电极、及蓄电元件 |
JP6810452B2 (ja) * | 2016-11-14 | 2021-01-06 | ナミックス株式会社 | 金属被覆粒子及び樹脂組成物 |
EP3503214A1 (en) * | 2017-12-22 | 2019-06-26 | Merck Patent GmbH | Solar cells |
CN112250107A (zh) * | 2020-10-21 | 2021-01-22 | 华北电力大学 | 一种单晶菱形二氧化钛纳米颗粒及其制备方法和二氧化钛浆料及其应用 |
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- 2009-06-19 WO PCT/JP2009/061220 patent/WO2009154274A1/ja active Application Filing
- 2009-06-19 CN CN2009801231903A patent/CN102066260A/zh active Pending
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US20120312370A1 (en) * | 2011-06-07 | 2012-12-13 | Mcgill University | Hybrid dye-sensitized solar cell photoanodes based on aqueous synthesized titanium dioxide |
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EP2292560A4 (en) | 2011-06-01 |
EP2292560B1 (en) | 2015-08-12 |
US9409790B2 (en) | 2016-08-09 |
CN102066260A (zh) | 2011-05-18 |
KR20110022684A (ko) | 2011-03-07 |
KR101332526B1 (ko) | 2013-11-22 |
EP2292560A1 (en) | 2011-03-09 |
US20110079276A1 (en) | 2011-04-07 |
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