WO2011065601A1 - Cellule solaire à colorant ayant couche d'absorbeur dans laquelle une pluralité d'oxydes métalliques de type nanotube ou nanotige sont déployés dans une seule direction, et son procédé de fabrication - Google Patents

Cellule solaire à colorant ayant couche d'absorbeur dans laquelle une pluralité d'oxydes métalliques de type nanotube ou nanotige sont déployés dans une seule direction, et son procédé de fabrication Download PDF

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WO2011065601A1
WO2011065601A1 PCT/KR2009/006978 KR2009006978W WO2011065601A1 WO 2011065601 A1 WO2011065601 A1 WO 2011065601A1 KR 2009006978 W KR2009006978 W KR 2009006978W WO 2011065601 A1 WO2011065601 A1 WO 2011065601A1
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dye
sensitized solar
solar cell
transparent substrate
metal
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PCT/KR2009/006978
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English (en)
Korean (ko)
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허완수
이광훈
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숭실대학교 산학협력단
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Publication of WO2011065601A1 publication Critical patent/WO2011065601A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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 invention relates to a dye-sensitized solar cell, and more particularly, to a dye-sensitized solar cell having improved efficiency due to improved electron mobility and reduced electron loss.
  • the present invention is derived from a study carried out as part of the industry-university cooperation project in Seoul as follows.
  • the solar cell is a battery that generates electrical energy using solar energy, has the advantages of environmentally friendly, infinite energy source and long life.
  • solar cells include silicon solar cells, semiconductor compound solar cells, and dye-sensitized solar cells.
  • Dye-sensitized solar cells are solar cells in which dye molecules that absorb sunlight and convert them into electrons are adsorbed on semiconductor oxide nanoparticle electrodes that provide a large specific surface area.
  • Dye-sensitized solar cells have the advantage of low cost compared to other silicon solar cells and semiconductor compound solar cells.
  • FIG. 1 is a view schematically showing an example of a conventional dye-sensitized solar cell.
  • Dye-sensitized solar cells generally include a semiconductor electrode 10, an electrolyte layer 13, and a counter electrode 20.
  • the semiconductor electrode 10 includes a transparent substrate 11 and a light absorption layer 12, and the light absorption layer 12 includes metal oxide nanoparticles 12a and a dye 12b.
  • the counter electrode 20 includes a transparent substrate 21 and a catalyst layer 22.
  • FIG. 2 is a view schematically showing the operating principle of the dye-sensitized solar cell.
  • sunlight hits the dye 12b that is incident through the transparent substrate 11 and adsorbed onto the surface of the metal oxide nanoparticles 12a.
  • the metal oxide nanoparticles 12a are used as a scaffold to adsorb a large number of dye 12b molecules to a given cell surface area.
  • the sunlight hitting the dye 12b causes the dye 12b to be excited to emit electrons e ⁇ from the dye 12b.
  • Electrons (e ⁇ ) emitted from the dye 12b are directly injected into the conduction band of the metal oxide nanoparticles 12a and are moved to the transparent substrate 11 by a chemical diffusion gradient.
  • the dye 12b which has lost electrons obtains electrons by oxidizing iodine ions I ⁇ in the electrolyte layer 13 to 3 iodine ions I 3- . 3 iodine ions I 3-in the electrolyte mechanically diffuse to the counter electrode 20 and recover electrons lost by counter electrons flowing there through an external circuit.
  • the metal oxide nanoparticles 12a each have a size of about 15 to 25 nm, and the plurality of nanoparticles 12a are electrically formed by forming a three-dimensional network. A well-connected particle film of about 20 ⁇ m thick is formed.
  • the metal oxide nanoparticles 12a constitute an irregular polycrystalline network, electrons generated from the dye 12b molecules are transported to the transparent substrate 11 at a slow speed, or the metal oxide nanoparticles 12a are transported. There is a problem that disappears in conjunction with).
  • An object of the present invention is to form a metal oxide in which the dye molecules are adsorbed on the surface in the form of nanotubes, bridge nanotubes, nanorods or bridge nanorods and arrange them side by side in a direction perpendicular to the smooth surface of the transparent substrate Forming a thin film, thereby increasing the amount of light absorbed by the dye per unit area of the dye, while reducing the travel distance from the metal oxide to the transparent substrate to efficiently transfer electrons to provide a dye-sensitized solar cell with improved efficiency It is.
  • the present invention to solve the above problems,
  • a semiconductor electrode comprising a first transparent substrate and a light absorption layer disposed on one surface of the first transparent substrate;
  • the light absorption layer has a plurality of metal oxides having at least one type selected from the group consisting of nanotubes, bridge nanotubes, nanorods having an aspect ratio of 10 to 1000, and bridge nanorods having an aspect ratio of 10 to 1000, and adsorbed thereto. It provides a dye-sensitized solar cell comprising a dye.
  • the method of manufacturing a dye-sensitized solar cell between the step (c) and (d), the anodized metal oxide of the step (c) of the metal oxide Immersing in a solution containing the precursor and heating to form a plurality of metal oxides in the form of bridge nanotubes or bridge nanorods having an aspect ratio of 10 to 1000.
  • the coating of the metal is ion plating, magnetron sputtering, chemical vapor deposition, chemical vapor deposition (evaporation), spin coating (spin coating), thermal oxidation method ( thermal oxidation, computer jet printing technique, spray pyrolysis or photochemical deposition.
  • the coating of the metal is made by the metal is incident on the transparent substrate in the direction normal and inclined of the smooth surface, while the transparent substrate is rotated.
  • step (c) the anodic oxidation treatment of step (c) is performed in-situ.
  • the plurality of metal oxides are arranged side by side in a direction perpendicular to the smooth surface of the first transparent substrate (or transparent substrate).
  • the metal comprises at least one of Ti and its alloys.
  • the electrolyte used in the anodic oxidation treatment of step (c) includes hydrogen peroxide (H 2 O 2 ).
  • the electrolyte contains at least one ion selected from the group consisting of fluorine ion (F ⁇ ), chlorine ion (Cl ⁇ ) and sulfate ion (SO 4 2 ⁇ ).
  • the electrolyte used in the anodizing of step (c) includes fluorine ions.
  • the electrolyte layer is poly (vinylidene fluoride-co-poly (hexafluoropropylene)), polyacrylonitrile-based polymer, polyethylene oxide-based polymer and polyalkylacrylate-based polymer At least one selected from the group consisting of.
  • FIG. 1 is a cross-sectional view schematically showing the structure of a conventional dye-sensitized solar cell.
  • FIG. 2 is a view for explaining the operating principle of the dye-sensitized solar cell of FIG.
  • 3 and 4 are cross-sectional views schematically showing the structure of the dye-sensitized solar cell according to an embodiment of the present invention.
  • 5 and 6 are diagrams for explaining the operating principle of the dye-sensitized solar cell of Figures 3 and 4, respectively.
  • FIG. 7 is a SEM photograph showing a metal oxide in the form of nanotubes provided in the dye-sensitized solar cell of FIG. 3.
  • FIG. 8 is a SEM photograph showing a metal oxide in the form of a bridge nanotube provided in the dye-sensitized solar cell of FIG. 3.
  • FIG. 9 is a graph showing photocurrent-voltage characteristics of the dye-sensitized solar cells prepared in Examples 1-1 to 1-4, 2-1 to 2-4, and Comparative Examples 1 to 3.
  • FIG. 9 is a graph showing photocurrent-voltage characteristics of the dye-sensitized solar cells prepared in Examples 1-1 to 1-4, 2-1 to 2-4, and Comparative Examples 1 to 3.
  • 10 and 11 are SEM photographs showing metal oxides in the form of nanorods provided in the dye-sensitized solar cell of FIG. 4.
  • 12 and 13 are SEM photographs showing metal oxides in the form of bridge nanorods provided in the dye-sensitized solar cell of FIG. 4.
  • 3 and 4 are cross-sectional views schematically showing the structure of the dye-sensitized solar cell according to an embodiment of the present invention.
  • a dye-sensitized solar cell includes a semiconductor electrode 100, an electrolyte layer 103, and an opposite electrode 110.
  • the semiconductor electrode 100 includes a first transparent substrate 101 and a light absorption layer 102 disposed on one surface of the first transparent substrate 101.
  • the main material of the first transparent substrate 101 is not particularly limited as long as it has transparency, and for example, a glass substrate may be used.
  • a material for imparting conductivity to the transparent substrate 101 any material can be used as long as it has conductivity and transparency.
  • tin oxide for example, SnO 2
  • ITO indium tin oxide
  • the light absorption layer 102 includes a plurality of metal oxides 102a1 and a dye 102b adsorbed thereto.
  • the metal oxides 102a1 each have a nanotube or bridge nanotube shape.
  • nanotube refers to a tube shape having a diameter of several nm to several tens of nm
  • bridge nanotube refers to a shape in which the nanotubes are at least partially connected to each other by a bridge.
  • the light absorption layer 102 includes a plurality of metal oxides 102a2 and a dye 102b adsorbed thereto.
  • the metal oxides 102a2 each have a nanorod or bridge nanorod shape having an aspect ratio of 10 to 1000.
  • the aspect ratio of the metal oxide 102a2 in the form of a bridge nanorod means an aspect ratio of only the metal oxide 102a2 in the form of a nanorod except for the bridge.
  • the "nanorod” means a rod shape having a diameter of several nm to several tens of nm
  • the "bridge nanorod” means a form in which the nanorods are at least partially connected to each other by a bridge. If the aspect ratio is less than 200nm, the thickness of the nanorod film is ultra-thin, so the absolute value of the generated photocurrent is lowered, which is undesirable.
  • the metal oxides 102a1 and 102a2 may be disposed in parallel with each other in a direction perpendicular to the smooth surface of the first transparent substrate 101.
  • vertical or “side by side” does not mean only completely vertical or side by side, but also perpendicular or side by side to those of ordinary skill in the art in view of limitations in manufacturing technology in the art. It is a concept that includes a margin of error that can be recognized.
  • the present invention is not limited thereto, and the metal oxides 102a1 and 102a2 may have a direction perpendicular to the smooth surface of the first transparent substrate 101 (that is, the normal direction of the smooth surface) and a predetermined angle inclined direction. It may be arranged as.
  • the metal oxides 102a1 and 102a2 may have a semiconductor property, and may be selected from a compound semiconductor or a compound having a perovskite structure in addition to a single semiconductor represented by silicon.
  • the semiconductor is preferably an n-type semiconductor in which conduction band electrons become carriers under photo excitation to provide an anode current.
  • Specific examples of the semiconductor include TiO 2 (titanium dioxide), SnO 2 , ZnO, WO 3 , Nb 2 O 5 , TiSrO 3, and the like.
  • Particularly preferred semiconductors are anatase type TiO 2 .
  • the kind of semiconductor is not limited to these, These can be used individually or in mixture of 2 or more types.
  • the metal for forming the metal oxides 102a1 and 102a2 include Zn, Zr, Yr, Mo, In, Sc, W, Ti, Mn, Sn, Zr, V, Si, Cr, Mg, Al, Fe, Ba , Pb, La, Sr, Bi, Ta, Cu, Ca, Nb and at least one selected from the group consisting of alloys thereof.
  • the metal oxide having such a structure and structure is preferably a large surface area so that the dye adsorbed on the surface can absorb more light.
  • the particle size of the metal oxide is preferably 1 ⁇ m or less, more preferably 10 ⁇ 300nm, even more preferably 10 ⁇ 100nm.
  • the dye 102b can be used without particular limitation as long as it is generally used in the solar cell or photovoltaic field, but ruthenium complex is preferable.
  • ruthenium complex RuL 2 (SCN) 2 , RuL 2 (H 2 O) 2 , RuL 3 , RuL 2, etc. may be used (wherein L is 2,2′-bipyridyl-4,4′-dica). Carboxylates).
  • the dye 102b is not particularly limited as long as it has a charge separation function and exhibits a sensitive action. Therefore, in addition to the ruthenium complex, for example, xanthine-based pigments such as rhodamine B, rosebengal, eosin, and erythrosine, quinocyanine and kryptosh Basic dyes, such as cyanine pigment
  • xanthine-based pigments such as rhodamine B, rosebengal, eo
  • the thickness of the light absorption layer 102 including the metal oxides 102a1, 102a2 and the dye 102b is preferably 50 ⁇ m or less, more preferably 1 to 35 ⁇ m. That is, the light absorption layer 102 has a large series resistance for structural reasons, and an increase in series resistance leads to a decrease in conversion efficiency. It is possible to prevent the degradation of the conversion efficiency.
  • An electrolyte layer 103 is I - and comprises a reduced species, I - - / I 3 - oxidation as a source of ions is LiI, NaI, alkyl iodide or imidazolium iodide, etc. are used, 3-I Ions are produced by dissolving I 2 in a solvent.
  • a liquid such as acetonitrile or a polymer such as polyethylene oxide may be used.
  • Carbonates, nitrile compounds, alcohols and the like may be used as the liquid medium, and in particular, carbonates such as propylene carbonate and nitrile compounds such as acetonitrile and methoxy acetonitrile may be used.
  • polyacrylonitrile PAN
  • polyethylene oxide PEO
  • polyalkylacrylate poly (alkylacrylate)
  • poly (vinylidene fluoride) -co-poly (hexafluoropropylene) may be used as the polymer medium.
  • poly (vinylidene fluoride) -co-poly (hexafluoropropylene) may be used as the polymer medium. It is also possible to prepare and use a gel electrolyte by adding a gelator to the liquid electrolyte.
  • the counter electrode 110 includes a second transparent substrate 111 and a catalyst layer 112 disposed on the second transparent substrate 111 so as to face the light absorbing layer 102.
  • the second transparent substrate 111 may be formed of the same or similar material as that of the first transparent substrate 101 described above.
  • any conductive material may be used without limitation, but any insulating material may be used as long as a conductive layer (not shown) is disposed on the side facing the semiconductor electrode 100.
  • an electrochemically stable material is used as an electrode, and specifically, platinum, gold, carbon, etc. are used.
  • Dye-sensitized solar cell having the configuration as described above forms a metal oxide disposed in the light absorption layer of the semiconductor electrode in the form of nanotubes, bridge nanotubes, nanorods or bridge nanorods and a transparent substrate
  • a metal oxide disposed in the light absorption layer of the semiconductor electrode in the form of nanotubes, bridge nanotubes, nanorods or bridge nanorods and a transparent substrate
  • the ratio of light incident on the first transparent substrate of the semiconductor electrode to be absorbed and lost by the metal oxide before reaching the dye may be reduced compared to the prior art, thereby increasing the light absorption rate per unit area of the dye.
  • the optical efficiency can be improved by reducing the distance to the transparent substrate so that electrons can be efficiently transferred.
  • a first transparent substrate for a semiconductor electrode is prepared.
  • a metal is coated on one surface of the first transparent substrate.
  • the coating of the metal may be ion plating, magnetron sputtering, chemical vapor deposition, evaporation, spin coating, thermal oxidation, computer jet printing techniques ( computer jet printing technique, spray pyrolysis, photochemical deposition, or the like.
  • ion plating is one of the methods in the field of Physical Vapor Deposition, and a material (that is, a first transparent substrate) is charged into a high vacuum chamber, and then an electron beam gun is used. It is a method of melting the metal to be deposited using the vapor deposition on the surface of the material.
  • the magnetron sputtering method is a method belonging to the physical vapor deposition field like the ion plating method. Unlike the ion plating method, a metal target is used without an electron beam gun, and the metal target is converted into argon (Ar) ion. It is a method of depositing particles of a metal target that is thrown out to the material.
  • metal molecules (atoms) evaporated from the evaporation material immediately fly to and deposit on the surface of the plated body, whereas in the case of ion plating or magnetron sputtering, the evaporated molecules are formed earlier than the plated body.
  • the high-energy metal particles deposited on the film are electrically attracted to the plated body vigorously, thereby forming a much denser and harder film than vacuum deposition.
  • the coating of the metal adjusts the angle of incidence of the metal such that the metal is incident on the first transparent substrate in the direction normal to the inclined direction and the inclined direction while the first transparent substrate is rotated. It is preferable to rotate the first transparent substrate at a predetermined speed. In this way, the metal can be uniformly coated on the first transparent substrate.
  • titanium (Ti) as the metal and ion plating or magnetron sputtering method as the coating method.
  • the deposition thickness of the metal is preferably 1 ⁇ m or more. If the thickness is less than 1 ⁇ m, the thickness may be so thin that problems of anodic oxidation and corrosion resistance may occur.
  • the coated metal is then electrochemically anodized to form a plurality of metal oxides in the form of nanotubes or bridged nanotubes or to form a plurality of metal oxides in the form of nanorods or bridged nanorods.
  • the manufacturing cost can be reduced by performing a process of directly forming the metal oxide on the first transparent substrate, that is, an “in-situ” process.
  • the anodic oxidation treatment impregnates the coated metal in an electrolyte including HF, NH 4 F, HNO 3 , KF, H 2 SO 4 , NaF, DMF, DMSO, and / or EG, and then anodes the metal. It is made by supplying platinum or the like as a cathode at 0 to 50 ° C.
  • an oxide film grows on the metal surface of the anode to form an anodized film (ie, a metal oxide in the form of nanotubes or bridge nanotubes).
  • anodizing is performed at a constant voltage, the current gradually decreases with time, and only a very small current flows. That is, when anodizing is performed at a constant voltage, an oxide film having an insulation breakdown voltage corresponding to the voltage is formed, and then the growth of the oxide film is stopped.
  • the shape, diameter, and length of the metal oxide to be formed vary depending on the concentration of the electrolyte and voltage applied to the anodic oxidation.
  • the metal oxide in the form of nanotubes and the metal oxide in the form of bridge nanotubes are prepared through the same process until the anodic oxidation step, but in order to prepare the metal oxide in the form of bridge nanotubes, a sol containing a precursor of the metal oxide is used.
  • the solution must be used to grow nanotube metal oxides in the form of bridges. That is, the metal oxide in the form of bridge nanotubes can be prepared by immersing an anodized metal oxide (having nanotube form) in a sol solution of the metal oxide and heating the mixture to grow a metal oxide bridge. Can be.
  • the electrolyte used in the anodic oxidation treatment preferably contains fluorine ions.
  • the step of forming a plurality of metal oxides having a nanorod or bridge nanorod form by electrochemically anodizing the coated metal. Therefore, according to the manufacturing method of the present invention, it is possible to reduce the manufacturing cost by performing the process of forming the metal oxide directly on the first transparent substrate, that is, the "in-situ" process.
  • H 2 O 2 hydrogen peroxide
  • an oxide film grows on the metal surface of the anode to form an anodized film (that is, a metal oxide in the form of a nanorod or a bridge nanorod).
  • anodizing is performed at a constant voltage, the current gradually decreases with time, and only a very small current flows. That is, when anodizing is performed at a constant voltage, an oxide film having an insulation breakdown voltage corresponding to the voltage is formed, and then the growth of the oxide film is stopped.
  • the shape, diameter, and length of the metal oxide to be formed vary depending on the concentration of the electrolyte and voltage applied to the anodic oxidation.
  • the metal oxides in the form of nanorods and the metal oxides in the form of bridge nanorods are prepared through the same process until the anodic oxidation step, but in order to produce the metal oxides in the form of bridge nanorods, a sol containing a precursor of the metal oxide is used.
  • the solution must be used to grow nanorod metal oxides in the form of bridges.
  • the metal oxide in the form of a bridge nanorod can be prepared by immersing an anodized metal oxide (having a nanorod form) in a sol solution of the metal oxide and heating the mixture to grow a metal oxide bridge.
  • the electrolyte used in the anodic oxidation treatment preferably contains fluorine ions.
  • the formed metal oxide in the form of nanotubes, bridge nanotubes, nanorods, or bridge nanorods is heated to crystallize the particles.
  • This heat treatment is carried out at a temperature of 200 ⁇ 500 °C, whereby the formed metal oxide is conductive.
  • a counter electrode prepared in advance is disposed to face the metal oxide, and the electrolyte composition containing the redox electron pair is embedded and sealed to complete the dye-sensitized solar cell.
  • a titanium film having a diameter of 7 ⁇ m was formed on the indium doped tin oxide transparent conductor by a sputtering method. Subsequently, a titanium oxide was formed on the outer circumferential surface of the impregnated titanium film by impregnating a portion of the titanium film with an NH 4 F aqueous solution. At this time, the concentration of the NH 4 F aqueous solution was 0.5% by weight. Subsequently, a voltage of 20 V was applied for 30 minutes using the titanium film as an anode. Next, the anodized titanium oxide was heat-treated in air at a temperature of 450 to 500 ° C. for 30 minutes to pyrolyze and remove the residual electrolyte, thereby converting the titanium oxide crystal structure into an anatase type. As a result, a plurality of titanium oxides were obtained.
  • the formed titanium oxide was each shown to have a nanotube form as shown in FIG. Subsequently, the specimen was maintained at 80 ° C., and then dye adsorption was carried out in 0.3 mM [Ru (dcb) 2 (dfo)] (CN) 2 dye dye solution dissolved in methanol for 12 hours. Thereafter, the dye-adsorbed nanotube-type titanium oxide thick film was washed with methanol and dried at room temperature to prepare a semiconductor electrode.
  • a Pt layer was deposited on the indium-doped tin oxide transparent conductor by using a sputter, and a counter hole was manufactured by making a minute hole using a 0.75 mm diameter drill for electrolyte injection.
  • the two electrodes were bonded together by pressing a 60 ⁇ m-thick thermoplastic polymer film between the semiconductor electrode and the counter electrode and pressing at 100 ° C. for 9 seconds.
  • the redox electrolyte was injected through the micropores formed in the counter electrode, and the micropores were closed using a cover glass and a thermoplastic polymer film.
  • the redox electrolyte used was 0.62M 1,2-dimethyl-3-hexylimidazolium iodide (1,2-dimethyl-3-hexylimidazolium iodide), 0.5M 2-aminopyrimidine (2- aminopyrimidine), 0.1 M LiI and 0.05 M I 2 dissolved in an acetonitrile solvent were used.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 1-1, except that a voltage of 20 V was applied for 60 minutes, 120 minutes, and 200 minutes using the titanium film as an anode.
  • Anodized titanium oxide was prepared in the same manner as in the preparation of (1) semiconductor electrode of Example 1, and then the anodized titanium oxide was immersed in TiCl 4 + HCl sol solution, A dye-sensitized solar cell was manufactured in the same manner as in Example 1, except that the TiO 2 bridge was grown by heating for a time.
  • the formed titanium oxide was shown to each have a bridge nanotube form as shown in FIG.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 2-1, except that a voltage of 20 V was applied for 60 minutes, 120 minutes, and 200 minutes using the titanium film as an anode.
  • Example 2 a titanium oxide particle dispersion having a particle size of 20 to 25 nm was coated on an area of 1 cm 2 on the transparent conductor using a doctor blade method, and a heat treatment firing process was performed at 450 ° C. for 30 minutes.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 1 except that the porous titanium oxide thick film having a thickness of 2.5 ⁇ m was used.
  • a dye-sensitized solar cell was manufactured in the same manner as in Comparative Example 1-1, except that the thickness of the porous titanium oxide thick foil was changed to 4.2 ⁇ m and 7.3 ⁇ m, respectively.
  • the short-circuit current (Jsc) according to the thickness of the titanium oxide (T) was measured and shown in FIG. 9.
  • the titanium oxide thickness (T) and the short circuit current (Jsc) are listed as specific values in Table 1 below.
  • a xenon lamp (Oriel, 01193) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (Frunhofer Institute Solare Engeries systeme, Certificate No. C-ISE369, Type of material: Mono-). Si + KG filter).
  • the dye-sensitized solar cells of Examples 1-1 to 1-4 and 2-1 to 2-4 have the same thickness of titanium oxide by introducing metal oxides in the form of nanotubes and bridge nanotubes, respectively. That is, it can be seen that the current characteristic is improved with respect to the thickness of the light absorption layer. This is understood to be due to the increase in light absorption by the dye and the improvement of current due to the shortening of the transfer path of electrons generated in the dye.
  • Comparative Examples 1 to 3 when the metal oxide in the form of nanoparticles is introduced, it can be seen that the photocurrent generation is significantly reduced due to the light loss and the electron loss caused by the metal oxide.
  • a titanium film having a diameter of 5 ⁇ m was formed on the indium doped tin oxide transparent conductor by a sputtering method. Subsequently, a titanium oxide was formed on the outer circumferential surface of the impregnated titanium film by impregnating a portion of the titanium film in an aqueous solution of H 2 O 2 + TaCl 5 . At this time, the concentration of TaCl 5 in a 30 wt% H 2 O 2 aqueous solution was 5 mM. Subsequently, a voltage of 10 V was applied for 120 minutes using the titanium film as an anode. Next, the anodized titanium oxide was heat-treated in air at a temperature of 450 ° C. for 30 minutes to pyrolyze and remove the residual electrolyte, thereby converting the crystal structure of titanium oxide into an anatase type.
  • the formed metal oxides were each shown to have a nanorod shape as shown in FIGS. 10 and 11. Subsequently, after the specimen was maintained at 80 ° C., dye adsorption was performed for 0.3 hours in a 0.3 mM [Ru (dcb) 2 (dfo)] (CN) 2 dye dye solution dissolved in methanol. Thereafter, the dye-adsorbed nanorod titanium oxide thick film was washed with methanol and dried at room temperature to prepare a semiconductor electrode.
  • a Pt layer was deposited on the indium-doped tin oxide transparent conductor using a sputter, and a counter hole was manufactured by making a minute hole using a 0.75 mm diameter drill for electrolyte injection.
  • the two electrodes were bonded together by pressing a 60 ⁇ m-thick thermoplastic polymer film between the semiconductor electrode and the counter electrode at 100 ° C. for 9 seconds.
  • the redox electrolyte was injected through the micropores formed in the counter electrode, and the micropores were closed using a cover glass and a thermoplastic polymer film.
  • the redox electrolyte used was 0.62M 1,2-dimethyl-3-hexylimidazolium iodide (1,2-dimethyl-3-hexylimidazolium iodide), 0.5M 2-aminopyrimidine (2- aminopyrimidine), 0.1 M LiI and 0.05 M I 2 dissolved in an acetonitrile solvent were used.
  • Anodized titanium oxide was prepared in the same manner as in the preparation of (1) semiconductor electrode of Example 3, and then the anodized titanium oxide was immersed in TiCl 4 + HCl sol solution, A dye-sensitized solar cell was manufactured in the same manner as in Example 3, except that the TiO 2 bridge was grown by heating for a time.
  • the formed metal oxides were each shown to have a bridge nanorod shape as shown in FIGS. 12 and 13.
  • Example 3 a titanium oxide particle dispersion having a particle size of 20 to 25 nm was applied to a 1 cm 2 area on a transparent conductor using a doctor blade method, and a heat treatment firing process was performed at 450 ° C. for 30 minutes.
  • a dye-sensitized solar cell was manufactured in the same manner as in Example 3, except that the porous titanium oxide thick film having a thickness of 15 ⁇ m was used.
  • the photoelectric conversion quantum efficiency of the dye-sensitized solar cells prepared in Examples 3, 4 and Comparative Example 2 was measured and shown in FIG. 14.
  • the photoelectric conversion quantum efficiency refers to the extent to which incident photons react in the visible light region to generate current.
  • Photoelectric conversion quantum efficiency was measured using IPCE (incident photon-to-current conversion efficient, manufactured by PV Measurements) and the wavelength range was 350-800 nm.
  • the dye-sensitized solar cells of Examples 3 and 4 improve photoelectric conversion quantum efficiency by introducing metal oxides in the form of nanorods and bridge nanorods, respectively. This is understood to be due to the increase in light absorption by the dye and the improvement of current due to the shortening of the transfer path of electrons generated in the dye.
  • Comparative Example 2 when the metal oxide in the form of nanoparticles is introduced, it can be seen that the photoelectric conversion quantum efficiency is significantly low due to light loss and electron loss caused by the metal oxide.
  • the efficiency of the dye-sensitized solar cell can be improved by shortening the electron transport path.
  • a metal oxide film that is, a light absorption layer into a thin film
  • the light absorption rate of the dye can be improved.
  • the metal oxide film in-situ in-situ it is possible to simplify the manufacturing process of the dye-sensitized solar cell to reduce the manufacturing cost.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention porte sur une cellule solaire à colorant qui comprend une pluralité d'oxydes métalliques de type nanotube, nanotube ponté, et nanotige ou nanotige pontée, et sur son procédé de fabrication. La cellule solaire à colorant comporte : une électrode semi-conductrice qui comprend un premier substrat transparent et une couche d'absorbeur disposée sur un côté du premier substrat transparent ; une contre-électrode qui est disposée de façon séparée pour faire face à l'électrode semi-conductrice, et qui comprend un second substrat transparent et une couche de catalyseur disposée pour faire face à la couche d'absorbeur sur le second substrat transparent ; une couche d'électrolyte qui est intercalée entre l'électrode semi-conductrice et la contre-électrode, la couche d'absorbeur comprenant une pluralité d'oxydes métalliques qui sont d'au moins un type choisi dans un groupe qui comporte des nanotubes, des nanotubes pontés, des nanotiges ayant un rapport d'allongement de 10 à 1000, et des nanotiges pontées ayant un rapport d'allongement de 10 à 1000, et des colorants qui sont absorbés dans les oxydes métalliques. Ainsi, la cellule solaire à colorant augmente le rendement et réduit les coûts de fabrication.
PCT/KR2009/006978 2009-11-25 2009-11-25 Cellule solaire à colorant ayant couche d'absorbeur dans laquelle une pluralité d'oxydes métalliques de type nanotube ou nanotige sont déployés dans une seule direction, et son procédé de fabrication WO2011065601A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324305A (zh) * 2011-06-20 2012-01-18 清华大学 用于染料敏化太阳能电池的复合结构对电极及其制备方法

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KR20060033158A (ko) * 2004-10-14 2006-04-19 한국전기연구원 탄소나노튜브 전극을 이용한 염료감응형 태양전지
KR100849220B1 (ko) * 2007-04-16 2008-07-31 요업기술원 기판 위에 자기 정렬된 고밀도 타이타니아 나노튜브 및나노와이어의 제조방법.
US20090000663A1 (en) * 2007-04-04 2009-01-01 Sungkyunkwan University Foundation For Corporate Collaboration Dye-sensitized solar cell and method of manufacturing the same
KR20090022956A (ko) * 2007-08-31 2009-03-04 현대자동차주식회사 산화티타늄 나노튜브를 이용한 염료감응형 태양전지와 그제조방법

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Publication number Priority date Publication date Assignee Title
KR20060033158A (ko) * 2004-10-14 2006-04-19 한국전기연구원 탄소나노튜브 전극을 이용한 염료감응형 태양전지
US20090000663A1 (en) * 2007-04-04 2009-01-01 Sungkyunkwan University Foundation For Corporate Collaboration Dye-sensitized solar cell and method of manufacturing the same
KR100849220B1 (ko) * 2007-04-16 2008-07-31 요업기술원 기판 위에 자기 정렬된 고밀도 타이타니아 나노튜브 및나노와이어의 제조방법.
KR20090022956A (ko) * 2007-08-31 2009-03-04 현대자동차주식회사 산화티타늄 나노튜브를 이용한 염료감응형 태양전지와 그제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324305A (zh) * 2011-06-20 2012-01-18 清华大学 用于染料敏化太阳能电池的复合结构对电极及其制备方法

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