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WO2013036052A2 - Photoélectrode destinée à une cellule solaire à colorant, procédé de fabrication de la photoélectrode et cellule solaire à colorant utilisant la photoélectrode - Google Patents

Photoélectrode destinée à une cellule solaire à colorant, procédé de fabrication de la photoélectrode et cellule solaire à colorant utilisant la photoélectrode Download PDF

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Publication number
WO2013036052A2
WO2013036052A2 PCT/KR2012/007194 KR2012007194W WO2013036052A2 WO 2013036052 A2 WO2013036052 A2 WO 2013036052A2 KR 2012007194 W KR2012007194 W KR 2012007194W WO 2013036052 A2 WO2013036052 A2 WO 2013036052A2
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Prior art keywords
oxide
photoelectrode
dye
polymer
metal oxide
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PCT/KR2012/007194
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English (en)
Korean (ko)
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WO2013036052A3 (fr
WO2013036052A8 (fr
Inventor
고민재
이도권
김봉수
김홍곤
최인석
유기천
이진아
김경곤
Original Assignee
한국과학기술연구원
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Priority to CN201280053894.XA priority Critical patent/CN103918051B/zh
Priority claimed from KR1020120098724A external-priority patent/KR101437046B1/ko
Publication of WO2013036052A2 publication Critical patent/WO2013036052A2/fr
Publication of WO2013036052A3 publication Critical patent/WO2013036052A3/fr
Publication of WO2013036052A8 publication Critical patent/WO2013036052A8/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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

  • Photoelectrode for dye-sensitized solar cell manufacturing method thereof and dye-sensitized solar cell using same
  • the present invention provides a dye-sensitized solar cell light including a porous membrane composed of metal oxide nanoparticle metal oxide-photosensitive material-polymer having excellent durability and mechanical strength against external stimuli (UV, chemical, thermal, laminar) and excellent electrical properties.
  • the present invention relates to an electrode, a method of manufacturing the same, and a dye-sensitized solar cell using the same. [Technique to become background of invention]
  • Dye-sensitized solar cells are representative of the photoelectrochemical solar cells published by Gratzel et al. In Switzerland in 1991, and generally use a photosensitive dye that absorbs visible light and a wide bandgap energy. It consists of a metal oxide nanoparticle having, a counter electrode catalyzed by platinum (Pt), and an electrolyte filled therebetween.
  • the composition including the photosensitive dye and the metal oxide nanoparticles acts as a semiconductor electrode (ie, a photoelectrode).
  • the dye-sensitized solar cell is cheaper to manufacture than conventional silicon solar cells or compound semiconductor solar cells, and its efficiency is higher than that of organic solar cells. In order to commercialize such dye-sensitized solar cells, it is necessary to have long-term safety against external stimuli (UV, chemical, heat, lamination).
  • the semiconductor electrode (ie photoelectrode) used in the conventional dye-sensitized solar cell has the structure of the photosensitive material broken by external stimulus (UV, chemical, heat, impact), or the photosensitive material and metal nano. Cracks occur easily when an external force (shock) occurs due to a disconnection between oxides (chemical) or a structural characteristic of interconnection between metal oxides.
  • the conventional photoelectrode also causes a problem that the electrode from the substrate is peeled off. There are many problems, such as the need for the development of a new photoelectrode having excellent electrical characteristics as well as durability against external stimuli.
  • an object of the present invention is a dye-sensitized solar cell light that can secure excellent mechanical strength and electrical properties as well as excellent durability against external stimulation by a simple process using a polymer. It is to provide an electrode and a method of manufacturing the same.
  • Another object of the present invention is to provide a dye-sensitized solar cell photoelectrode and a method for manufacturing the same, which can be applied to various substrates regardless of the type of substrate.
  • Still another object of the present invention is to provide a solar cell having high photoelectric efficiency and securing durability and mechanical strength of a semiconductor film layer of a dye-sensitized solar cell using the photoelectrode as a semiconductor electrode.
  • the present invention includes a conductive substrate, and a porous membrane formed thereon, wherein the porous membrane includes a metal oxide nanoparticle layer adsorbed with a photosensitive material and a polymer layer formed on the surface thereof.
  • the polymer layer may have a form surrounding the surface of the metal oxide nanoparticles to which the photosensitive material is adsorbed.
  • the dye-sensitized solar cell photoelectrode is a UV lamp of 500W / m 2 intensity, the reduction rate (%) of the photoelectric conversion effect after UV irradiation for 30 minutes is less than 70% compared to the initial efficiency before UV irradiation, 0.1 to 80% by weight basic solution , The photoelectric conversion efficiency reduction rate (%) after immersion in alcohol solution or water is 70% or less of the initial efficiency before chemical solution immersion, The reduction rate (%) of photoelectric conversion efficiency after storage at 60 to 12 CTC may be 703 ⁇ 4> or less than the initial efficiency.
  • the conductive substrate may include a glass substrate coated with a conductive film, a flexible plastic substrate, or a metal substrate.
  • the conductive substrate is a flexible plastic substrate, and can provide a photoelectrode having a reduction ratio of photoelectric conversion efficiency after 100 to 1000 bending tests using a cylindrical bending tester having a diameter of 10 mm or less and 70% or less of the initial efficiency. have.
  • the porous membrane may have a porosity of 30 to 80% and a thickness of 1 to 100 ⁇ m.
  • the present invention (a) forming a porous membrane comprising a metal oxide nanoparticles on a conductive substrate;
  • the present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectrode.
  • a dye-sensitized solar cell comprising the dye-sensitized photoelectrode.
  • the conventional method of manufacturing a semiconductor electrode has a problem such as poor durability of the film of the solar cell.
  • the applicant has proceeded a method of forming a film by blending a high molecule in the nanoparticle metal oxide layer (Korean Patent Publication No. 201 0088310; L
  • the method is to proceed to the nanoparticles
  • the polymer occupies the place where the dye can adsorb and the dye adsorption amount is reduced, and the polymer as the insulator can coat the surface of the metal nanoparticles and interfere with the electron transfer.
  • the method consists of ensuring the durability of the outer layer of the flexible dye-sensitized solar cell.
  • the present invention breaks the structure of the photosensitive material by external stimulus (UV, chemical, heat, impact), or breaks the connection between the photosensitive material and the metal nanooxide (chemical), or the metal oxide.
  • the present invention provides a dye-sensitized solar cell excellent in mechanical strength capable of withstanding external strong mechanical stratification and a manufacturing method thereof.
  • the present invention provides a method for manufacturing a photoelectrode, which can be applied to any type of substrate, such as a glass substrate or a flexible substrate.
  • nano described in the specification of the present invention means nano-scale, and may include micro units.
  • nanoparticle described herein includes all types of particles having a nanoscale.
  • a conductive substrate, and a porous membrane formed thereon the porous membrane comprises a metal oxide nanoparticle layer adsorbed on the photosensitive material and a polymer layer formed on the surface
  • a battery photoelectrode is provided.
  • the photoelectrode for a dye-sensitized solar cell of the present invention is a conductive substrate 103 coated with a conductive film 102 on the transparent substrate 101, and a metal oxide nanoparticle layer and a polymer worm adsorbed a photosensitive material formed thereon It consists of a porous membrane 107 containing (FIG. 1).
  • 1 is a schematic view showing a cross-sectional view of a dye-sensitized photoelectrode according to the present invention.
  • the photoelectrode of the present invention is a UV lamp of 500W / m 2 intensity for 30 minutes after the UV irradiation photoelectric conversion efficiency reduction rate (3 ⁇ 4) is less than 70% of the initial efficiency before UV irradiation,
  • the photoelectric conversion efficiency reduction rate (%) after immersion in basic solution, alcohol solution or water at 0.1 to 80 weight 3 ⁇ 4 concentration is 70% or less of the initial efficiency before chemical solution immersion, and the photoelectric conversion efficiency reduction rate after storage at 60 to 120 ° C. (%) Is characterized by less than 70% of the initial efficiency before storage at the temperature.
  • the photoelectrode is a UV lamp of 500W / m 2 intensity for 30 minutes after the UV irradiation photoelectric conversion efficiency (%) is 1 to 70%, more preferably 1 to 50% compared to the initial efficiency before UV irradiation,
  • the photoelectric conversion efficiency reduction rate (%) after immersion in a basic solution, alcohol solution or water at a concentration of 0.1 to 50% by weight is 1 to 70%, more preferably 1 to 50% compared to the initial efficiency before chemical solution immersion,
  • the percent reduction in photoelectric conversion efficiency after storage at 60 to 120 ° C is stored at this temperature It may be 1 to 70%, more preferably 1 to 50% compared to the initial efficiency before.
  • the photoelectrode of the present invention is characterized in that the porous membrane includes a metal oxide nanoparticle layer on which a photosensitive material is adsorbed and a polymer layer formed on the surface thereof. That is, the porous membrane referred to in the present invention may mean a composite in which an inorganic material (metal oxide nanoparticle layer) is used together with an organic material (polymer layer) and has a connection relationship. In addition, the porous membrane of the present invention may be configured in the order of application of nanoparticle metal oxide-photosensitive material-polymer.
  • the invention using the existing metal oxide nanoparticles and polymer forms a complex of metal oxide-polymer, but since the polymer is bleeded during the manufacturing process, the metal oxide nanoparticles and the polymer are all entangled and dye is adsorbed thereon. Has a modified form.
  • the polymer solution is coated and heat treated on the metal oxide nanoparticles to which the photosensitive material is adsorbed, whereby the photosensitive material as the porous membrane is adsorbed.
  • the surface of the metal oxide nanoparticle layer may have a form including a polymer layer.
  • the polymer layer may have a form surrounding the surface of the metal oxide nanoparticles to which the photosensitive material is adsorbed (FIG. 2). 2 is a schematic view of a polymer coated on the surface of the photoelectrode according to the present invention.
  • the polymer layer 106 is a photosensitive material (ie, a dye). ) Is formed surrounding the surface of the adsorbed metal oxide nanoparticles, and as the polymer layer is formed on the surface, the portion where the photosensitive material is not adsorbed can be filled with the polymer layer to improve electrical properties. Can be.
  • the present invention can prevent the dye adsorption amount decrease, increase the electron transfer effect to improve the electrical properties.
  • the durability and mechanical strength against external stimuli UV, chemical, heat, impact
  • the present invention exhibits excellent durability even if there is an external stimulus under the above-described conditions, it is possible to maintain excellent electrical properties.
  • porous membrane of the present invention may be penetrated between the metal oxide nanoparticles in which a portion of the polymer is adsorbed by the photosensitive material by the coating process. Therefore, the present invention can increase the adhesion with the substrate than conventional.
  • the present invention can prevent the structure of the photosensitive material from being broken by UV or heat. Also, in general, the chemical solution breaks the bond between the metal oxide nanoparticles and the photosensitive material.
  • the photoelectrode of the present invention is easily disconnected between the photosensitive material and the metal oxide nanoparticles even after the chemical solution is immersed. I do not lose.
  • the present invention can prevent cracks due to excellent durability and strength even if the interconnection structure between the metal oxide (interconnect ion structure) characteristics, it is possible to solve the problem of separation of the substrate and the electrode.
  • the basic solution in the chemical solution may be an aqueous solution of 1 to 80% by weight containing a common alkali metal.
  • the alcohol solution may be an aqueous solution containing alcohol having 1 to 6 carbon atoms.
  • Water is general, and may include both ultrapure or crude water that has undergone ion exchange resins.
  • the substrate applied in the present invention can be used as long as the substrate used in the solar cell, there is a feature that can use both a transparent conductive substrate or a flexible substrate.
  • the conductive substrate may include a glass substrate coated with a conductive film, a flexible plastic substrate, or a metal substrate.
  • the transparent conductive substrate When used in the present invention, it may exhibit more excellent durability, mechanical strength, and electrical properties than the conventional one.
  • the present invention may use a flexible plastic substrate in order to further improve bending characteristics as well as durability, mechanical properties and electrical properties.
  • the dye-sensitized solar cell to which the flexible substrate is applied is a mobile phone, wear It is becoming a focus of interest in that it can be used for self-layering, clothes, hats, auto glass, buildings, etc. of power supplies required for the next generation PC industry, such as flexible PCs. Accordingly, in the present invention, in the photoelectrode having the above-described configuration, the transparent conductive electrode can be replaced with a flexible substrate, thereby providing excellent bending characteristics and excellent photoelectric conversion efficiency, and provide an optical electrode having excellent durability. Can be.
  • the conductive substrate may be a flexible plastic substrate, wherein the plastic substrate exhibits flexibility and includes a porous membrane of the specific configuration described above.
  • the photoelectrode has a diameter of 10 mm or less, more preferably 5 to 10 mm, and a photoelectric conversion efficiency reduction rate (3 ⁇ 4>) after 100 to 1000 bending tests using a cylindrical bending tester is 70% or less compared to the initial efficiency, more preferably. It may be up to 50%. Therefore, since the photoelectrode has excellent bending characteristics even if it is bent several times, it is possible to prevent durability deterioration due to external lamination and to maintain excellent electrical characteristics.
  • the bending tester can use all the usual bending test equipment, for example, a cylindrical bending tester having the diameter range can be used.
  • the bending method for the photoelectrode during the bending test may be proceeded by a method well known in the art. For example, the photoelectrode is placed in a circular bending tester, and one side of the photoelectrode is fixed by a mechanical method and the other One side may be bent several times or both sides of the photoelectrode may be repeatedly bent and stretched at the same time.
  • the plastic substrate is polyethylene terephthalate; Polyethylene naphthalate; Polycarbonate; Polypropylene; Polyimide; Triacetylcells; Polyether sulfone; Organic modified silicates of three-dimensional network structure formed by the hydrolysis and condensation reaction of one or more organometallic alkoxides selected from the group consisting of methyl trie special silane, ethyl trie special silane and propyl trie silane; Copolymers thereof; And one or more selected from the group consisting of these mixtures.
  • the metal substrate is iron, stainless steel, egg Any one selected from the group consisting of aluminum, titanium, nickel, copper and tin can be used.
  • the conductive film may include Sn0 2 : F, IT0, a metal electrode having an average thickness of 1 to 100Onm, a metal nitride, a metal oxide, a carbon compound, or a conductive polymer, but is not limited to the above material and is well known in the art.
  • Known conventional conductive films can be formed on the transparent substrate.
  • the metal nitride may be a nitride of a Group IVB metal element including titanium (Ti), zirconium (Zr), and hafnium (Hf); Nitrides of group VB metal elements including niobium (Nb), tantalum (Ta) and barnacle (V); From the group consisting of nitrides, aluminum nitrides, gallium nitrides, indium nitrides, silicon nitrides, germanium nitrides and combinations thereof of group VIB metal elements including chromium (Cr), molybdenum (Mo) and tungsten (W) You can select one or more.
  • group IVB metal element including titanium (Ti), zirconium (Zr), and hafnium (Hf); Nitrides of group VB metal elements including niobium (Nb), tantalum (Ta) and barnacle (V); From the group consisting of nitrides, aluminum nitrides, gallium
  • the metal oxide may be tin (Sn) oxide, antimony (Sb), niobium (Nb) or fluorine-doped tin (Sn) oxide, indium (In) oxide, tin-doped indium (In) oxide, zinc (Zn) oxide , Aluminum (A1), Boron (B), Gallium (Ga), Hydrogen (H), Indium (In), Yttrium (Y), Titanium (Ti), Silicon (Si) or Tin (Sn) doped zinc ( Zn) oxide, magnesium (Mg) oxide, cadmium (Cd) oxide, magnesium zinc (MgZn) oxide, indium zinc (InZn) oxide, copper aluminum (CuAl) oxide, silver (Ag) oxide, gallium (Ga) Oxides, Zinc Tin Oxide (ZNSN0), Titanium Oxide (TI02) and Zinc Indium Tin (ZIS) Oxide, Nickel (Ni) Oxide, Rhodium (Rh) Oxide, Rucenium (Ru) Ox
  • the carbon compound may be used by selecting one or more from the group consisting of activated carbon, graphite, carbon nanotubes, carbon blocks, graphene, or a mixture thereof.
  • the conductive polymer is PED0T (poly (3, 4-ethylenedioxythiophene))-
  • PSS poly (styrenesulfonate)
  • polyaniline ⁇ CSA pentacene
  • polyacetylene P3HT (poly (3-nucleothiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxy-4- (0-dispersed 1) -2,5-phenylene-vinylene), Poly indole, polycarbazole, polypyridazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene, polyfluorene, polypyridine, polypyri, polysulfuride and copolymers thereof It can be used by selecting one or more from the group consisting of.
  • the polymer used in the polymer layer is polyurethane, polyethylene oxide, polyvinylpyridone, polypropylene oxide, polyethylene glycol, chitosan, chitin, polyacrylamide, polyvinyl alcohol, polyacrylic acid, cellulose, ethyl cellulose , Silicone containing polyhydroxyethyl methacrylate, polymethyl methacrylate, polysaccharide, polyamide, polycarbonate, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyethylene naphthalate, polydimethylsiloxane It may include at least one polymer selected from the group consisting of polymers, isoprene, butadiene rubber and derivatives thereof. However, the polymer material is not particularly limited, and all known polymers may be used. In addition, the average thickness of the polymer layer may be 1 to 100 nm, more preferably 1 to 50 nm, most preferably 1 to 20 nm.
  • the metal oxide nanoparticle layer on which the photosensitive material is adsorbed may include tin (Sn) oxide, antimony (Sb), niobium (Nb) or fluorine-doped tin (Sn) oxide, indium (In) oxide, tin-doped indium ( In) oxide, zinc (Zn) oxide, aluminum
  • A1 boron (B), gallium (Ga), hydrogen (H), indium (In), yttrium (Y), titanium (Ti), silicon (Si) or tin (Sn) doped zinc (Zn) oxide ,
  • Mg magnesium oxide
  • Cd Cadmium oxide
  • MgZn Magnesium zinc oxide
  • Indium zinc (InZn) oxide Copper aluminum (CuAl) oxide
  • ZnSnO titanium oxide
  • Ti02 zinc indium tin
  • ZIS zinc indium tin
  • Ni nickel oxide
  • rhythm (Rh) oxide ruthenium oxide
  • iridium (Ir) oxide copper oxide
  • Cobalt (Co) Oxide Tungsten (W) Oxide
  • the metal oxide nanoparticles may include titanium oxide nanoparticles.
  • the photosensitive material may include a photosensitive organic material capable of absorbing visible light having a band gap of 1 eV to 3.1 eV, a photosensitive inorganic material, a photosensitive organic-inorganic composite material, or a mixture thereof. Can be.
  • the porous membrane is a metal oxide nanoparticle layer and a polymethyl methacrylate polymer layer
  • a photosensitive material is adsorbed, a metal oxide nanoparticle layer and a polyvinylpyridone polymer layer, or photosensitive
  • the porous membrane may be a porous membrane having a porosity of 30 to 80> and a thickness of 1 to 100 ⁇ m.
  • a method of manufacturing the above-described dye-sensitized photoelectrode including.
  • a dye-sensitized solar cell comprising the photoelectrode.
  • the method of manufacturing the dye-sensitized photoelectrode of the present invention is preferably prepared according to the method shown in FIG. 3 is a dye-sensitized photoelectric according to the present invention It is a schematic of the process for demonstrating the manufacturing method of a pole and the manufacturing method of the dye-sensitized solar cell containing said electrode: electrode. 4 is a cross-sectional view of the dye-sensitized solar cell according to the present invention.
  • the present invention prepares a conductive substrate 103, and forms a porous membrane 104 including metal oxide nanoparticles thereon (FIG. 3A).
  • the conductive substrate 103 may use a transparent conducting oxide (TCO) coated with a conductive film 102 on the transparent substrate 101, and may be replaced with the above-described flexible substrate or metal substrate, if necessary. It is possible.
  • TCO transparent conducting oxide
  • the photosensitive material is adsorbed on the surface of the porous membrane 104 to form a porous membrane 105 including metal oxide nanoparticles on which the photosensitive material is adsorbed, thereby providing a basic photoelectrode.
  • the polymer solution is coated directly on the porous membrane 105 including the metal oxide nanoparticles to which the photosensitive material is adsorbed, and the metal oxide nanoparticle layer to which the photosensitive material is adsorbed and the polymer layer formed on the surface thereof.
  • the dye-sensitized photoelectrode 110 including the porous membrane 107 is manufactured (Fig. 3 (c)).
  • porous membrane 107 Although the configuration of the porous membrane 107 is not specifically illustrated in FIG. 3C, it may have the configuration of FIG. 2.
  • the electrolyte 130 is injected and sealed with the polymer adhesive 140.
  • Dye-sensitized solar cell is manufactured (Fig.
  • the structure of the counter electrode 120 may be manufactured as well known in the art.
  • the counter electrode may include a transparent substrate 101, a conductive film 102 and a catalyst layer 121 formed on the substrate 101. Through these steps, the present invention can complete the structure of the dye-sensitized solar cell shown in FIG.
  • low or high temperature firing may be applied depending on whether a binder is used in the paste manufacturing process including the metal oxide nanoparticles when forming the porous membrane 104 in step (a).
  • both low temperature or high temperature firing may be applied depending on the type of the substrate.
  • the porous membrane 104 is coated with a paste containing metal oxide nanoparticles on one surface of the conductive substrate 103 and heat treated, and then subjected to low temperature (150 ° C. or lower) or high temperature (temperature 150 ° C. or higher) conditions. It can be formed by firing at.
  • the step of forming the porous membrane (a) after (i) coating a low-temperature baking paste containing metal oxide nanoparticles and a solvent on a conductive substrate and heat-treated for 1 to 2 hours at a temperature of 20 to 15CTC, Or (ii) heat treating the high temperature baking paste including the metal oxide nanoparticles, the binder resin, and the solvent on the conductive substrate for 1 to 2 hours at a temperature of 450 to 500 ° C.
  • the present invention when firing at a low temperature, is a low-temperature firing paste coated on a conductive substrate for 1 to 2 hours at a temperature of 20 to 150 ° C, 150 ° C or less, preferably 100 to 150 It can be baked at a low temperature of ° C to form a porous membrane.
  • the conductive substrate preferably includes a flexible substrate.
  • low temperature firing means firing in a state of relatively low temperature with respect to the existing high temperature firing temperature exceeding 15CTC.
  • high temperature firing means firing in excess of the above 150 ° C.
  • the present invention may form a porous membrane by heat treatment at a temperature of 450 to 500 ° C for 1-2 hours after coating the high temperature baking paste on the conductive substrate.
  • the substrate is preferably a glass substrate or the like.
  • the paste baked at low and high temperatures may be prepared by a method well known in the art, and the method is not particularly limited.
  • the low temperature baking paste may be prepared by mixing the metal oxide nanoparticles with a solvent to prepare a colloidal solution in which the metal oxide nanoparticles are well dispersed in 10 to 50%, and then removing the solvent with a distiller.
  • the mixing ratio and type of the metal oxide nanoparticles and the solvent are not particularly limited and may be used by a method well known in the art.
  • the solvent may be ethanol, methanol, terpineol, lauric acid or the like. It is preferable that the metal oxide nanoparticles used for preparing the paste have a particle size of 10 to lOOran.
  • the high temperature baking paste is mixed with metal oxide nanoparticles in a solvent to prepare a colloidal solution having a viscosity of 5X10 4 to 5X10 5 cps in which the metal oxide is dispersed, and then mixed by adding a binder resin, and the solvent is removed by a distillation.
  • a binder resin may be polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose.
  • the solvent may be ethanol, methanol, terpineol, lauric acid and the like.
  • metal oxide nanoparticles used to prepare the porous membrane a metal oxide well known in the art may be used, and for example, the same metal oxide as described above may be used.
  • the coating method of the paste a method such as screen printing may be used, but the method is not particularly limited, and any conventional coating method such as a doctor bleed may be used.
  • (b) adsorbing the photosensitive material includes immersing the substrate on which the porous membrane 104 including the metal oxide nanoparticles is formed in a solution containing the photosensitive material for 1 to 24 hours.
  • the present invention forms a primary photoelectrode.
  • the bran 12 porous film refers to a metal oxide nanoparticle layer on which a photosensitive material is adsorbed.
  • a photosensitive material having the same band 3 ⁇ 4 as described above may be used.
  • photosensitive material examples include aluminum (A1), platinum (Pt), palladium (Pd), flow path product (Eu), lead (Pb), iridium (Ir), ruthenium (Ru) selenium (Se), telelide ( Te), sulfur (S) and may include an element selected from the group consisting of a complex thereof.
  • the method for preparing the photosensitive material-containing solution is not particularly limited and may be prepared by a method well known in the art.
  • the manufacturing of the photoelectrode for dye-sensitized solar cell is completed. That is, the present invention coated and dried the polymer solution on the primary photoelectrode that adsorbed the photosensitive material prepared through step (b), the metal oxide nanoparticle layer adsorbed the photosensitive material of Figure 2 and its surface A secondary photoelectrode having a porous membrane 107 including the polymer layer 106 formed thereon may be manufactured.
  • a general method such as spin coating is used to form a polymer layer, and the polymer solution can be dried at a low temperature of about 25 ° C., thus providing a photoelectrode for dye-sensitized solar cell in a very easy manner. There are features that can be.
  • the coating of the polymer solution can be carried out using a spin coating, a slit coating or a dip coating method, it is more preferable to use spin coating.
  • the thickness of the polymer solution is not limited, but may be 1 to lOOrai.
  • the present invention can be subjected to a step of infiltrating the polymer into the nanoparticle metal oxide for about 1 to 10 minutes after dropping the polymer solution on the metal oxide nanoparticle layer adsorbed by the photosensitive material prior to spin coating when forming the polymer layer have.
  • a portion of the polymer is a gold with a photosensitive material adsorbed
  • the adhesion to the substrate may be improved as compared to the case where the oxide nanoparticle layer is directly intercalated and coated with a polymer solution.
  • drying may be performed for 1 to 30 minutes at a temperature of 20 to 150 ° C or less. Preferably, the drying may be carried out for 30 minutes within 1 minute at a low temperature of 20 ° C to 30 ° C. If necessary, rapid drying may be performed at about 100 to 150 degrees for about 1 minute.
  • the polymer solution is preferably a colloidal solution in which 0.01 to 50% by weight of the polymer is dispersed in the solvent 'based on the total polymer solution. Since the polymer solution may be prepared by a method well known in the art, the method is not particularly limited.
  • the polymer may be mixed with a solvent to prepare a colloidal solution in which the polymer is well dispersed at 0.01-50 wt%, more preferably 0.01 to 10 weight 3 ⁇ 4 through uniform stirring.
  • the mixing ratio of the high molecule and the solvent may be changed as necessary, but preferably proceeds to the ratio.
  • the polymer is different from the concept used in the conventional general paste manufacturing, it is characterized in that the last remaining in the electrode.
  • Such polymer materials are not particularly limited in their kind, and materials well known in the art may be used.
  • the polymer is polyurethane, polyethylene oxide (PEO, Polyethylenoxide), polypropylene oxide, polyvinylpyrrolidone, EG, Polyethyleneglycol, chitosan, chitin, poly Polyacrylamide, Polyvinyl Alcohol, Polyacrylic Acid, Ethyl Cellulose, Polyhydroxyethyl Methacrylic Acid (PHEMA, Polyhydroxyethylmethacryl icacid), Polymethylmethacrylate
  • polycarbonate Polyethylene, Polypropylene (Polypropylene), polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), silicon-containing polymers including polydimethylsiloxane (PDMS), isoprene, butadiene rubber and derivatives thereof It may include one or more polymer compounds, more preferably two or more polymers.
  • the polymer may be polymethyl methacrylate (PMMA, Polymethylmethacrylate), polyvinylpyrrolidone (PVP, Polyvinylpyrrolidone), or polyethylene oxide (PE0, Polyethylenoxide), these may be used as one or two or more Can be used in combination.
  • the present invention depending on the type of the polymer, it is possible to further secure the UV stability and chemical stability.
  • polymers such as PVP and PMMA-PVP polymers can be used.
  • polymers such as PMMA and PMMA-PVP may be used.
  • the type of solvent used to prepare the polymer solution is also not limited.
  • the solvent may dissolve ethane, methane, terpineol, lauric acid, ethyl acetate, nucleic acid, toluene, and the like. Any solvent can be used.
  • the structure of the dye-sensitized solar cell can be obtained by performing step (d) of FIG.
  • Step (d) may be performed by using a counter electrode, an electrolyte, and the like in a general method except for disposing the photoelectrode of the present invention.
  • the present invention is to arrange the counter electrode to face each other at a predetermined interval with the photo-electrode for the dye-sensitized solar cell manufactured by the above-described method, and to fill the space between the photo electrode and the counter electrode with an electrolyte, The photoelectrode and the counter electrode are sealed with a polymer adhesive, thereby manufacturing a solar cell.
  • Such a solar cell is a transparent substrate, as shown in Figure 3 (d) and 4
  • a photoelectrode 110 including a porous membrane 107 including a formed polymer layer 106;
  • a counter electrode (120) comprising a transparent substrate (101), a conductive film (102) coated on the substrate, and a catalyst layer (121) formed on the conductive film;
  • a polymer adhesive layer 140 for sealing the photoelectrode and the counter electrode.
  • the catalyst layer may be formed by a conventional method.
  • the catalyst layer may be formed by forming a nanoparticle metal film using Pt to form a portion of the counter electrode.
  • These catalyst layers are platinum (Pt), activated carbon, graphite, carbon nanotubes, carbon black, U-shaped semiconductors, PED0T (poly (3, 4-ethylenedioxythiophene))-PSS (poly (styrene) Sulfonates)), polyaniline-CSA, pentacene, polyacetylene, P3HT (poly (3-nucleothiophene), polysiloxane carbazole, polyaniline, polyethylene oxide, (poly (1-methoxyl 4- (0- Dispersed 1) -2,5—phenylene-vinylene), polyindole, polycarbazole, polypyridazine, polyisothianaphthalene, polyphenylene sulfide, polyvinylpyridine, polythiophene,
  • the substrate 101 forming the counter electrode 120 may use the same transparent conductive electrode, transparent plastic substrate, or a metal substrate such as stainless steel or Ti, which is used in manufacturing the photoelectrode.
  • the thickness of the substrate and the catalyst layer of the counter electrode in the present invention is not particularly limited, and may include a structure well known in the art.
  • the electrolyte 130 is shown in a simple filled state for convenience of description in FIGS. 1 and 2, but is actually uniformly inside the porous membrane 107 in the space between the photoelectrode 110 and the counter electrode 120. Can be dispersed.
  • the electrolyte may be a redox derivative, a polymer gel electrolyte containing a polymer or an inorganic particle, an organic hole conductor (HCM, spiro-OMeTAD) and a P-type semiconductor.
  • HCM organic hole conductor
  • spiro-OMeTAD spiro-OMeTAD
  • the electrolyte includes an oxidation-reduction derivative which serves to receive electrons from the counter electrode by oxidation-reduction and transfer them to the dye of the photoelectrode, and is not particularly limited as long as it can be used in a conventional dye-sensitized solar cell.
  • the oxidation-reduction derivatives are selected from the group consisting of electrolytes containing iodine (I), bromine (Br), cobalt (Co), cyanide sulfide (SCN-) and selenium sulfide (SeCN-). It is preferable that 1 or more types are selected.
  • the polymer gel electrolyte containing the polymer may contain one or more polymers selected from the group consisting of polyvinylidene fluoride-co-polynuclear fluoropropylene, polyacrylonitrile, polyethylene oxide and polyalkyl acrylate.
  • the polymer gel electrolyte containing no dentifier may contain one or more inorganic particles selected from the group consisting of silica and Ti3 ⁇ 4 nanoparticles.
  • the electrolyte may include an organic hole conductor (HCM, spiro-OMeTAD) and a P-type semiconductor (CuSCN).
  • the solar cell may further include an adhesive which is a heat-sealed polymer film 140 or a paste for sealing the semiconductor electrode and the counter electrode, and the type of the adhesive may be a special material because the adhesive may be used. It is not limited.
  • the photosensitive at a low temperature (approximately 25 ° C) easily through a spin coating method can be produced with a photo-electrode is gongjil film comprising a nanoparticle metal oxide layer and the polymer layer adsorbed male substance.
  • This method can be expected to increase the current value due to the higher dye adsorption than blending existing polymers.
  • the electrode thus formed has a structure in which the photosensitive material is broken by an external stimulus (UV, chemical, heat, impact), or between the photosensitive material and the metal nanooxide, compared to an electrode composed only of an existing inorganic material.
  • cracks can easily occur when external forces (layer stratification) occur due to disconnected (chemical) or interconnected structural properties between metal oxides.
  • a dye-sensitized solar cell having excellent durability can be effectively produced.
  • FIG. 1 is a schematic view showing a cross-sectional view of a dye-sensitized photoelectrode according to the present invention.
  • Figure 2 is a schematic diagram of a polymer coated on the surface of the photoelectrode according to the present invention.
  • Figure 3 is a schematic diagram of a process for explaining a method for manufacturing a dye-sensitized photoelectrode according to the present invention and a method for manufacturing a dye-sensitized solar cell including the photoelectrode.
  • FIG. 4 is a cross-sectional view of the dye-sensitized solar cell according to the present invention.
  • FIG. 5 is a carbon electron probe micro-analyser (EPMA) result for viewing polymer powder in metal oxide nanoparticles of Example 1 and Comparative Example 1.
  • FIG. 6 is a transmission electron microscope (TEM) result of a polymer coating state on surfaces of metal oxide nanoparticles of Example 1 and Comparative Example 1 of the present invention.
  • Example 7 is a photograph comparing Examples 1 to 3 and Comparative Example 1 of the present invention after immersing in NaOH solution for 10 minutes to desorption of the photosensitive material.
  • Example 9 is a graph comparing the reduction of the efficiency of the dye-sensitized solar cell after the external bending test of Example 4 and Comparative Example 2 using a flexible substrate.
  • FIG. 10 is a graph illustrating comparison of voltage and charge rate curves of dye-sensitized solar cells according to external bending tests of Example 4 and Comparative Example 2 of the present invention.
  • FIG. 10 is a graph illustrating comparison of voltage and charge rate curves of dye-sensitized solar cells according to external bending tests of Example 4 and Comparative Example 2 of the present invention.
  • Example 1 [Specific contents to carry out invention] Hereinafter, the Example about this invention is described. However, the following examples are only illustrated to aid the understanding of the present invention, and the scope of the present invention is not limited to these examples.
  • Example 1
  • a conductive glass substrate ((Philkington, Inc., material: FT0, thickness 2.2 cm, ⁇ ⁇ / sq, substrate including 101 and 102 in FIG. 3) was prepared.
  • a metal oxide nanoparticle paste including 18.5 wt% of titanium oxide nanoparticles (average particle diameter: 20 nm), 0.05 wt% of a polymer for binder (ethylsalose), and a residual amount of solvent (Terpineol) was placed on the glass substrate. After application (using a doctor blade method), the substrate was heat-treated at 500 ° C. for 30 minutes to form a porous membrane (thickness: 10 / m) containing metal oxide nanoparticles.
  • ruthenium (Ru) series photosensitive dye N719 bis (tetrabutyla ⁇ onium) -cis— (di thiocyanato-N, N '-bis (4-carboxylato-4' -car boxy 1 ic aci d ⁇ 2, 2'- Bipyridine) ruthenium (II)
  • N719 bis (tetrabutyla ⁇ onium) -cis— (di thiocyanato-N, N '-bis (4-carboxylato-4' -car boxy 1 ic aci d ⁇ 2, 2'- Bipyridine)
  • ruthenium (II) The complex electrode was immersed in an ethanol solution containing 0.5 mMol for 1 hour at 50 ° C. to adsorb the photosensitive dye on the surface of the nanoparticles of the porous metal oxide layer.
  • the polymethyl methacrylate (PMMA) polymer was dissolved in ethyl acetate (EA) to prepare a polymer solution (colloid solution containing 5 wt. PMMA).
  • EA ethyl acetate
  • the polymer was allowed to penetrate the nanoparticle metal oxide for about 1 to 10 minutes, followed by spin coating at 2000 rpm. Drying was carried out for 10 minutes at a silver temperature of ° C. Through this process, the polymer layer was formed on the surface of the porous membrane of the dye-adsorbed nanoparticle metal oxide to manufacture a photoelectrode.
  • the counter electrode prepared a transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed. After dropping a solution of 2-propane in which chloroplatinic acid (PtCl 6 ) is dissolved on the transparent conductive oxide layer of the substrate, a platinum layer was formed by heat treatment at 400 ° C. for 20 minutes to prepare an anode-based electrode.
  • PtCl 6 chloroplatinic acid
  • a dye-sensitized solar cell was prepared by injecting and sealing an acetonitrile electrolyte containing PMIK1—methyl-3-propyliraidazolium iodide (0.7M) and I 2 (0.03M) in the space between the photoelectrode and the counter electrode. Prepared.
  • a conductive glass substrate ((Philkington, Inc., material: FT0, thickness 2.2 cm, ⁇ ⁇ / sq, substrate including 101 and 102 in FIG. 3) was prepared.
  • a titanium oxide nanoparticle (average particle diameter: 20 nm) was coated on the glass substrate with a metal oxide nanoparticle paste containing 18.5 weight 0.05 wt% of a polymer for binder (ethyl cellulose) and a residual solvent (Terpineol) ( After using the doctor blade method, the substrate was heat-treated at 500 ° C. for 30 minutes to form a porous membrane (thickness: 10) containing metal oxide nanoparticles.
  • polyvinylpyridone (PVP) polymer was dissolved in 2-propanol to prepare a polymer solution (colloid solution containing 5 wt% of PVP). After dropping the prepared polymer solution on the dye-adsorbed metal oxide nanoparticle layer After 1 minute to 10 minutes to allow the polymer to penetrate the nanoparticle metal oxide, spin coating was carried out at a speed of 2000 rpm and dried for 10 minutes at a temperature of 25 ° C. Through this process, the polymer layer was formed on the surface of the porous membrane of the dye-adsorbed nanoparticle metal oxide to manufacture a photoelectrode.
  • PVP polyvinylpyridone
  • the counter electrode prepared a transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed. After dropping a solution of 2-propane in which chloroplatinic acid (H 2 PtCl 6 ) is dissolved on the transparent conductive oxide layer of the substrate, heat treatment is performed at 400 ° C. for 20 minutes to form a platinum layer, thereby preparing an anode-based electrode. It was.
  • Dye-sensitized solar cell by injecting and sealing acetonitrile electrolyte containing PMII (l-methyl-3-propylimidazolium iodide, 0.7M) and 12 (0.03M) in the space between the photoelectrode and the counter electrode was prepared.
  • PMII l-methyl-3-propylimidazolium iodide
  • a conductive glass substrate (PhUkington, FTO, 2.2 cm thick,? / Sq, substrate including 101 and 102 of FIG. 3) was prepared.
  • a metal oxide nanoparticle paste containing 18.5 wt% of titanium oxide nanoparticles (average particle diameter: 20 nm), 0.05 wt% of a polymer for binder (ethyl cellulose), and a residual amount of solvent (Terpineol) was placed on the glass substrate.
  • the substrate was heat treated at 500 ° C. for 30 minutes to form a porous membrane (thickness: 10 / mi) containing metal oxide nanoparticles : ruthenium (Ru) )
  • Photosensitive dye N719 bis (tetrabutylammonium) -cis-
  • the polymethyl methacrylate (PMMA) polymer was dissolved in ethyl acetate (EA) to prepare a polymer solution (colloidal solution containing 5 wt% of PMMA).
  • EA ethyl acetate
  • the polymer was allowed to penetrate the nanoparticle metal oxide for about 1 to 10 minutes, followed by spin coating at 2000 rpm. Drying was carried out for 10 minutes at a temperature of ° C.
  • polyvinylpyridone (PVP) polymer was dissolved in 2-propanol to prepare a polymer solution (colloid solution containing 5 wt% of PVP).
  • the polymer After dropping the prepared polymer solution on the dye-adsorbed metal oxide nanoparticle layer, the polymer was allowed to penetrate the nanoparticle metal oxide for about 1 to 10 minutes, and then spin-coated at 2000 rpm. Drying was carried out for 10 minutes at a temperature of 25 ° C. Through this process, the polymer layer was formed on the surface of the porous membrane of the dye-adsorbed nanoparticle metal oxide to manufacture a photoelectrode.
  • the counter electrode prepared a transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed. After dropping a 2-propanol solution in which chloroplatinic acid (3 ⁇ 4PtCl 6 ) was dissolved on the top- ground conductive oxide layer of the substrate, a platinum layer was formed by heat treatment at 400 ° C. for 20 minutes to prepare an anode-based electrode.
  • Dye-sensitized solar cell is injected by injecting and sealing acetonitrile electrolyte containing PMII (l-methyl-3-propylimidazolium iodide, 0.7M) and I 2 (0.03M) in the space between the photoelectrode and the counter electrode.
  • the battery was prepared.
  • a conductive glass substrate (Philkington, FTO, 2.2 cm thick, ⁇ / sq, substrate including 101 and 102 of FIG. 3) was prepared.
  • a metal oxide nanoparticle paste including 18.5 wt% of titanium oxide nanoparticles (average particle diameter: 20 nm), 0.05 wt% of a binder polymer (ethylcellulose), and a residual amount of solvent (Terpineol) was coated on the glass substrate. After coating (using a doctor blade method), the substrate was heat-treated at 500 ° C. for 30 minutes to form a porous membrane (thickness: 10 / m) containing metal oxide nanoparticles.
  • the ruthenium-based photosensitive dye N719 bis (tetrabutylaramonium) -cis- (dithi ocyanat o to N, N'-bis (4-carboxy 1 at o-4 '-car boxy lie ac id ⁇ 2 , 2') Ethane containing 0.5 mM bipyridine) ruthenium (II) was immersed in the solution at 50 ° C. for 1 hour to adsorb the photosensitive dye on the surface of the nanoparticles of the porous metal oxide layer.
  • the counter electrode prepared a transparent glass substrate on which a fluorine-doped tin oxide transparent conductive oxide layer was formed. After dropping the 2-propanol solution in which chloroplatinic acid (3 ⁇ 4PtCl 6 ) is dissolved on the transparent conductive oxide layer of the substrate, a platinum layer was formed by heat treatment at 400 ° C. for 20 minutes to prepare an anode-based electrode.
  • Dye-sensitized solar cell is injected by injecting and sealing acetonitrile electrolyte containing PMII (l-methyl-3-propylimidazolium iodide, 0.7M) and I 2 (0.03M) in the space between the photoelectrode and the counter electrode.
  • the battery was prepared.
  • a solar cell was used on a flexible substrate.
  • the substrate in the experimental method of Example 1 and Comparative Example 1 A plastic substrate (peccell company, material: PEN / IT0, thickness 200i / m, 15Q / sq) was used.
  • the metal oxide paste was prepared into a uniform colloidal solution by stirring a solution obtained by dispersing 8 g of Ti0 2 nanoparticles (average particle size 20 nm) in 200 ml of ethanol (40 minutes / 450 rpm) using a mechanical stirrer.
  • a distillation apparatus and concentrated (rotary evaporator) to prepare a paste by distillation of the solvent to 170 rpm in the 50 ° C.
  • the paste was coated on a plastic substrate ( ⁇ / ⁇ ) by using the doctor blade method, and then heat-treated at 100 ° C. for 2 hours to remove the solvent to prepare an electrode having a thickness of 6 // m.
  • the substrate used for the counter electrode was a film coated with a Pt / Ti alloy having a thickness of 30 nm (Peccell Technologies, Inc., PEN, 18 / m thick, 5Q / sq).
  • Comparative Example 2 only the substrate is changed to the plastic substrate in Comparative Example 1 as described above.
  • Comparative Example 1 in which the polymer (PMMA) is not included at all has low carbon density and no polymer distribution.
  • the coating was carried out with a solution containing 5% by weight of polymer (PMMA) as in Example 1, it can be seen that the carbon density is increased and the polymer is evenly distributed.
  • the energy conversion efficiency was measured by 1.5AM 100mW / cm2 solar simulator (composed of Xe lamp [1600W, YAMASHITA DENS0], AMI.5 filter, and Keithley SMU2400). It was calculated using the formula.
  • J is the ⁇ -axis value of the conversion efficiency curve
  • V is the X-axis value of the conversion efficiency curve
  • J SC and Voc are intercept values of each axis.
  • UV lamp of 500W / m 2 intensity was irradiated to photoelectrode of Example 1-3 and Comparative Example 1 for 30 minutes, and then sal was made. conversion efficiency) was measured. The results after UV irradiation are shown in Table 2.
  • FIG. 7 is a photograph comparing Examples 1 to 3 and Comparative Example 1 of the present invention after immersion in 1M NaOH solution for 10 minutes to detect desorption of a photosensitive material.
  • UV and chemical stability are different.
  • In order to secure UV stability it is necessary to secure stability using PVP and PMMA-PVP polymer, and to secure chemical stability, it is necessary to secure chemical stability using PMMA and PMMA-PVP polymer.
  • Example 4 In order to see the mechanical safety of the photoelectrode of the dye-sensitized solar cell, the cells of Example 4 and Comparative Example 2 were made and the energy conversion efficiency according to the bending test was measured.
  • the bending test (bending test) is performed by performing a physical bending test in a conventional manner for 100 to 1000 times for each photoelectrode using a cylindrical bending tester having a diameter of 7 mm shown on the left side of FIG. It was. The results are shown in FIG.
  • Example 4 As shown in the external bending test results of Example 4 and Comparative Example 2, as shown in Figure 9, the coating on the dye adsorption metal oxide nanoparticle layer using a polymer solution in the manufacture of the flexible photoelectrode (Example 4) There was a big difference in the results of the case with and without (Comparative Example 2). That is, when comparing the characteristics of the cell (cell) of Example 4 and the results of Comparative Example 2, Comparative Example 2, which does not contain a high molecule at 200 bends did not operate at all as the efficiency is 0%. In contrast, the cells of Example 4 exhibited an efficiency of about 80%. Therefore, the present invention can implement a solar cell having a stable photoelectric efficiency and high photoelectric efficiency in the case of the flexible dye-sensitized solar cell applied to the flexible substrate as well as the above-described glass substrate.
  • Experimental Example 8
  • Example 4 was measured the open voltage and the fill factor according to the bending test obtained under AM 1.5G 1 Sun conditions. The results are shown in FIG. 10. In addition, experiments were carried out using a cylindrical bending tester having a diameter of 7 mm as in Experimental Example 7.
  • Example 2 As can be seen from the result of the external bending test of FIG. 10, the coating of the dye adsorption metal oxide nanoparticle layer using a polymer solution during the manufacture of the flexible photoelectrode. There was a big difference in the results of what was done (Example 2) and otherwise (Comparative Example 2). That is, comparing the characteristics of the cell of Example 4 with the results of Comparative Example 2, Comparative Example 2, which was not coated with a polymer when 200 bends, had an efficiency of 0% and did not operate at all. On the other hand, the sal of Example 4 showed a very high efficiency depending on the content of the polymer.
  • a photoelectrode including a porous membrane or a nanoparticle metal oxide-polymer composite including a metal oxide nanoparticle layer easily absorbed by a photosensitive material and a polymer layer formed on the surface thereof is manufactured by a spin coating method. can do.
  • the electrode thus formed may be broken in the structure of the photosensitive material by external stimulus (UV, chemical, heat, lamella) (U heat), or the connection between the photosensitive material and the metal nanooxide (chemical) or metal oxide.
  • porous membrane containing metal oxide nanoparticles adsorbed on the photosensitive material and a polymer layer formed on the surface thereof Catalyst layer : Counter electrode : Electrolyte

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Abstract

La présente invention a trait à une photoélectrode destinée à une cellule solaire à colorant, à un procédé de fabrication de la photoélectrode et à une cellule solaire à colorant utilisant la photoélectrode. Plus particulièrement, la présente invention a trait à une photoélectrode destinée à une cellule solaire à colorant et à un procédé de fabrication de la photoélectrode, laquelle photoélectrode comprend un film poreux (une couche d'oxyde métallique à nanoparticules), qui est formé sur un substrat conducteur et qui est constitué d'une couche polymère de matériau photosensible d'oxyde métallique à nanoparticules, ce qui permet de la sorte d'obtenir une durabilité supérieure contre la stimulation extérieure, une résistance mécanique supérieure et des caractéristiques électriques supérieures.
PCT/KR2012/007194 2011-09-06 2012-09-06 Photoélectrode destinée à une cellule solaire à colorant, procédé de fabrication de la photoélectrode et cellule solaire à colorant utilisant la photoélectrode WO2013036052A2 (fr)

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CN113130211A (zh) * 2021-03-17 2021-07-16 北京工业大学 一种高染料吸附量染料敏化太阳能电池光阳极及制备方法
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KR101034640B1 (ko) * 2009-01-30 2011-05-16 한국과학기술연구원 염료감응 태양전지용 나노입자 금속산화물-고분자의 복합체를 포함하는 광전극과 그 제조방법, 및 이를 이용한 염료감응 태양전지
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WO2015016399A1 (fr) * 2013-07-29 2015-02-05 서울대학교산학협력단 Photo-électrode de pile solaire à pigment photosensible comprenant un film semi-conducteur en ba-sn-m-o
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