WO2012148213A2 - Structure poreuse stratifiée à base d'oxyde de métal de transition, procédé pour la préparer, photoélectrode ayant ladite structure et cellule solaire à colorant dotée de ladite photoélectrode - Google Patents

Structure poreuse stratifiée à base d'oxyde de métal de transition, procédé pour la préparer, photoélectrode ayant ladite structure et cellule solaire à colorant dotée de ladite photoélectrode Download PDF

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Publication number
WO2012148213A2
WO2012148213A2 PCT/KR2012/003283 KR2012003283W WO2012148213A2 WO 2012148213 A2 WO2012148213 A2 WO 2012148213A2 KR 2012003283 W KR2012003283 W KR 2012003283W WO 2012148213 A2 WO2012148213 A2 WO 2012148213A2
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WO
WIPO (PCT)
Prior art keywords
transition metal
metal oxide
oxide structure
sacrificial layer
pores
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PCT/KR2012/003283
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English (en)
Korean (ko)
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WO2012148213A3 (fr
Inventor
문준혁
조창열
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서강대학교산학협력단
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Publication of WO2012148213A2 publication Critical patent/WO2012148213A2/fr
Publication of WO2012148213A3 publication Critical patent/WO2012148213A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • 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
    • H01G9/2059—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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application includes a hierarchical porous transition metal oxide structure, a method of manufacturing the hierarchical porous transition metal oxide structure, a hierarchical porous photoelectrode including the hierarchical porous transition metal oxide structure, and the hierarchical porous photoelectrode. It relates to a dye-sensitized solar cell.
  • the first sacrificial layer may be formed by spin coating or casting a solution containing the first polymer colloidal particles on the substrate, but is not limited thereto.
  • the heat firing process may be performed at a temperature of about 400 °C to about 800 °C, but is not limited thereto.
  • Another aspect of the present application provides a photoelectrode comprising a layered porous transition metal oxide structure according to the present application formed on a conductive transparent substrate.
  • the hierarchical porous transition metal oxide structure according to the present application can increase the light absorption efficiency by enabling light scattering by forming a structure having a large pore of the micrometer unit size, thereby ultimately improving the efficiency of the dye-sensitized solar cell Can contribute to
  • FIG. 1 is a schematic diagram of a layered porous transition metal oxide structure 100 according to an embodiment of the present application
  • Figures 2a to 2f is a manufacturing process of the layered porous transition metal oxide structure 100 according to an embodiment of the present application Schematic diagram for.
  • the base material 5 is prepared.
  • the substrate 5 is not particularly limited, and for example, the substrate 5 may be a conductive transparent substrate, but is not limited thereto.
  • the conductive transparent substrate is prepared by depositing a conductive transparent electrode on a transparent substrate.
  • the transparent substrate may be used without particular limitation as long as it is a material having transparency to allow incidence of external light.
  • a glass substrate or a transparent polymer substrate may be used.
  • the first transition metal oxide is Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and combinations thereof It may be to include an oxide of the transition metal selected from the group consisting of, but is not limited thereto.
  • the first transition metal oxide structure 30 may include titanium dioxide, and particularly, when the first transition metal oxide structure 30 includes titanium dioxide having an anatase crystallinity, it may be usefully applied as a photocatalyst, a photoelectrode, a sensor, and the like. Can be.
  • the size of the first pore 25 may be about 1 ⁇ m to about 1,000 ⁇ m, or about 10 ⁇ m to about 1,000 ⁇ m, or about 100 ⁇ m to about 1,000 ⁇ m, or about 1 ⁇ m to about 800 ⁇ m, Or about 1 ⁇ m to about 600 ⁇ m, or about 1 ⁇ m to about 400 ⁇ m, or about 1 ⁇ m to about 200 ⁇ m, or about 1 ⁇ m to about 100 ⁇ m.
  • the solvent used to remove the first sacrificial layer 15 may include a solvent capable of dissolving and removing the first polymer colloidal particles 10 according to the type of the first polymer colloidal particles 10. Can be used by selecting enemy.
  • the solvent may include an organic solvent, and may include, for example, toluene, benzene, chloroform, dimethylformamide (DMF), tetrahydrofuran, or the like, but is not limited thereto.
  • step D the second polymer colloidal particles 50 smaller than the size of the first pores 25 are injected into the first pores 25 arranged in three dimensions of the formed first transition metal oxide structure 30.
  • a second sacrificial layer 55 (FIG. 2D).
  • the second sacrificial layer 55 is formed by injecting second colloidal particles 50 having a nanometer size into the first pores 25 arranged in three dimensions of the first transition metal oxide structure 30. It may be, but is not limited thereto.
  • the second sacrificial layer 55 has a first pore 25 structure in which the colloidal particles 50 of the second polymer are arranged in three dimensions of the first transition metal oxide structure 30 by spin coating. It may be formed by being arranged inside, but is not limited thereto.
  • the second sacrificial layer 55 formed according to the step D is then a mold for forming the second transition metal oxide structure 70 having the second pores 65 of nanometer unit size arranged in three dimensions Used as
  • the second polymer colloidal particles 50 may have a size in nanometers, for example, several nanometers to several hundred nanometers, or tens of nanometers to several hundred nanometers in size. It may be, but is not limited thereto.
  • the size of the second polymer colloidal particles 50 may range from about 1 nm to about 1,000 nm, or from about 10 nm to about 1,000 nm, or from about 100 nm to about 1,000 nm, or from about 1 nm to about 800. nm, or about 1 nm to about 600 nm, or about 1 nm to about 400 nm, or about 1 nm to about 200 nm, or about 1 nm to about 100 nm.
  • the method may further include fixing the substrate 5 to a vacuum, but is not limited thereto.
  • the method may further include spin coating before removing the second sacrificial layer 55. It is not limited. The addition of such spin coating is to more uniformly inject the second transition metal oxide precursor 60 into the second sacrificial layer 55. The additional spin coating may be performed after injecting the solution including the second transition metal oxide precursor 60 or the second transition metal oxide nanoparticle into the second sacrificial layer 55, but is not limited thereto. It is not. The addition of such spin coating is to more uniformly inject the second transition metal oxide precursor 60 or the second transition metal oxide nanoparticles into the second sacrificial layer 55.
  • the second transition metal oxide is Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and combinations thereof It may be to include an oxide of the transition metal selected from the group consisting of, but is not limited thereto.
  • the second transition metal oxide structure 70 may include titanium dioxide, and in particular, when the second transition metal oxide structure 70 includes titanium dioxide having an anatase crystallinity, it may be usefully applied as a photocatalyst, a photoelectrode, a sensor, and the like. Can be.
  • the method may further include adsorbing a photosensitive dye on the formed layered porous transition metal oxide structure 100.
  • the layered porous transition metal oxide structure 100 according to the present application to which the photosensitive dye is adsorbed may be used as a photoelectrode.
  • the layered porous transition metal oxide structure 100 is immersed in a solution containing a photosensitive dye, so that the photosensitive dye is internal and external surfaces, eg, pores, of the layered porous transition metal oxide structure 100. It can be coated by adsorption on the surface.
  • the first pores 25 arranged in three dimensions formed by the first sacrificial layer 15 may have a size in a micrometer unit, and the second arranged in three dimensions formed by the second sacrificial layer 55.
  • the pores 65 may have a size in nanometers, but are not limited thereto.
  • the layered porous transition metal oxide structure 100 according to the present invention increases the specific surface area to increase the adsorption amount of the dye, thereby contributing to increasing the energy conversion efficiency of the solar cell when used as a photoelectrode for a dye-sensitized solar cell do.
  • a conductive transparent substrate was formed by forming a conductive ITO transparent electrode on the glass substrate.
  • a blocking layer including titanium dioxide was formed on the conductive transparent substrate.
  • the barrier layer containing titanium dioxide was formed by dipping the conductive transparent substrate in an aqueous 40 mM TiCl 4 solution and leaving it in an oven at 70 ° C. for 30 minutes. Thereafter, a layered porous transition metal oxide structure was formed on the blocking layer and a photosensitive dye was adsorbed to form a photoelectrode.
  • photosensitive dye molecules were adsorbed onto the obtained layered porous transition metal oxide structure.
  • N719 dye a ruthenium-based dye molecule
  • the ruthenium-based dye molecule N719 was dispersed in anhydrous propanol and adjusted to a concentration of 0.3 mM.
  • the formed photoelectrode was soaked for one day to adsorb the dye, followed by washing and drying to absorb the photosensitive dye.
  • a photoelectrode including a hierarchical porous titanium dioxide structure was prepared.
  • an electrolyte was injected between the photoelectrode and the counter electrode on which the platinum layer was formed.
  • the electrolyte may also penetrate into the pores of the photoelectrode including the hierarchical porous titanium dioxide structure.
  • the electrolyte may be prepared by mixing several components. In the present embodiment, a liquid electrolyte having an iodine-based redox pair is used.
  • Lithium iodide Lithium iodide
  • I 2 iodine
  • TBP 4-tert-butylylpyridine
  • 1-butyl-3-methyl imidazolium 1-butyl-3-methyl imidazolium was dissolved in acetonitrile (ACN) and used to prevent leakage of electrolyte solution.
  • ACN acetonitrile

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne une structure poreuse stratifiée à base d'oxyde de métal de transition, comprenant : une première structure à base d'oxyde de métal de transition ayant des premiers pores agencés de manière tridimensionnelle ; et une seconde structure à base d'oxyde de métal de transition formée à l'intérieur desdits premiers pores, la seconde structure ayant des seconds pores plus petits que lesdits premiers pores, les seconds pores étant agencés de manière tridimensionnelle. La présente invention concerne également un procédé de préparation de ladite structure poreuse stratifiée à base d'oxyde de métal de transition, une photoélectrode poreuse stratifiée ayant ladite structure poreuse stratifiée à base d'oxyde de métal de transition et une cellule solaire à colorant dotée de ladite photoélectrode poreuse stratifiée.
PCT/KR2012/003283 2011-04-28 2012-04-27 Structure poreuse stratifiée à base d'oxyde de métal de transition, procédé pour la préparer, photoélectrode ayant ladite structure et cellule solaire à colorant dotée de ladite photoélectrode WO2012148213A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110039970A KR101312335B1 (ko) 2011-04-28 2011-04-28 계층형 다공성 전이금속 산화물 구조체, 상기의 제조 방법, 상기를 포함하는 광전극, 및 상기 광전극을 포함하는 염료감응형 태양전지
KR10-2011-0039970 2011-04-28

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WO2012148213A2 true WO2012148213A2 (fr) 2012-11-01
WO2012148213A3 WO2012148213A3 (fr) 2013-01-17

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KR101401394B1 (ko) * 2012-12-28 2014-05-30 전자부품연구원 박막형 금속 산화물 역오팔 구조 제조방법

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KR101451114B1 (ko) * 2012-11-12 2014-10-17 서강대학교산학협력단 염료감응 태양전지용 광전극, 이의 제조 방법, 및 이를 포함하는 염료감응 태양전지
KR101465204B1 (ko) * 2013-03-26 2014-11-26 성균관대학교산학협력단 염료감응 태양전지 및 이의 제조 방법
KR101524016B1 (ko) * 2013-09-24 2015-05-29 서강대학교산학협력단 탄소가 도핑된 금속 산화물-함유 다공성 구조체, 상기의 제조방법, 및 상기를 포함하는 광촉매
JP6316417B2 (ja) 2013-10-31 2018-04-25 エルジー・ケム・リミテッド 逆オパール構造の多孔性基材を含む電気化学素子用多孔性分離膜及びこの製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101401394B1 (ko) * 2012-12-28 2014-05-30 전자부품연구원 박막형 금속 산화물 역오팔 구조 제조방법

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WO2012148213A3 (fr) 2013-01-17
KR20120122020A (ko) 2012-11-07
KR101312335B1 (ko) 2013-09-27

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