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WO2012086377A1 - Cellule solaire à colorant et module de cellules solaires à colorant, ainsi que procédés pour leur production - Google Patents

Cellule solaire à colorant et module de cellules solaires à colorant, ainsi que procédés pour leur production Download PDF

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Publication number
WO2012086377A1
WO2012086377A1 PCT/JP2011/077613 JP2011077613W WO2012086377A1 WO 2012086377 A1 WO2012086377 A1 WO 2012086377A1 JP 2011077613 W JP2011077613 W JP 2011077613W WO 2012086377 A1 WO2012086377 A1 WO 2012086377A1
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Prior art keywords
dye
sensitized solar
solar cell
electrode
auxiliary electrode
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English (en)
Japanese (ja)
Inventor
山中　良亮
福井　篤
古宮　良一
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Sharp Corp
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Sharp Corp
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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
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • 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
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • 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, a dye-sensitized solar cell module, and a manufacturing method thereof.
  • Patent Document 1 a dye-sensitized solar cell applying photoinduced electron transfer of a metal complex is proposed as a new type of solar cell.
  • This dye-sensitized solar cell has a structure in which a photoelectric conversion layer that adsorbs a photosensitizing dye and has an absorption spectrum in the visible light region and an electrolytic solution are sandwiched between two glass substrates.
  • the two glass substrates have a first electrode or a second electrode formed on their surfaces.
  • the dye-sensitized solar cell described in Patent Document 1 has a structure in which an electrolytic solution is injected between the electrodes of two glass substrates, a small-area solar cell can be prototyped. It is difficult to produce a large-area solar cell. That is, when the area of one solar cell is increased, the generated current increases in proportion to the area, but the resistance in the in-plane direction of the first electrode increases, and accordingly, the internal series electric resistance as a solar cell increases. Increase. As a result, there arises a problem that the fill factor (FF) in the current-voltage characteristic during photoelectric conversion is lowered.
  • FF fill factor
  • Patent Document 2 proposes a dye-sensitized solar cell in which a collecting electrode 103 is formed on a first electrode 102.
  • FIG. 6A is a top view of the dye-sensitized solar cell of Patent Document 2
  • FIG. 6B is a cross-sectional view of the dye-sensitized solar cell of Patent Document 2 taken along AA. is there.
  • a grid-like current collecting electrode 103 made of an alloy of gold and silver is formed on the first electrode 102 as shown in FIG. By forming the current collecting electrode 103, electric resistance can be reduced.
  • Patent Document 3 discloses an attempt to reduce the current collecting resistance and increase the output current density per electrode unit area in FIGS. 7 (a) and 7 (b).
  • the dye-sensitized solar cells shown have been proposed.
  • FIG. 7A is a schematic cross-sectional view of the dye-sensitized solar cell shown in Patent Document 3
  • FIG. 7B shows another form of the dye-sensitized solar cell shown in Patent Document 3. It is a schematic diagram.
  • a photoelectric conversion layer 203 is formed on the first electrode 201, and the photoelectric conversion layer 203 (that is, the photoelectric conversion layer 203) is formed.
  • a collecting electrode 204 is formed on the surface opposite to the surface in contact with the first electrode 201. Further, as shown in FIG. 7B, the collecting electrode 204 is formed in a line shape. In this way, the short-circuit current density is improved by forming the collecting electrode 204 on the 5 cm square photoelectric conversion layer 203.
  • the dye-sensitized solar cell of Patent Document 3 has a problem that depending on the material of the current collecting electrode 204, the leakage current from the current collecting electrode 204 becomes large and the open circuit voltage decreases, resulting in an improvement in conversion efficiency. I found out there was a problem.
  • the present invention has been made in view of the above-described situation, and an object of the present invention is to provide a dye-sensitized solar cell and a dye that can effectively improve the FF, the short-circuit current value, and the open-circuit voltage value. It is to provide a sensitized solar cell module.
  • the dye-sensitized solar cell of the present invention includes a first electrode, a second electrode provided to face the first electrode, a photoelectric conversion layer in contact with the first electrode, and within the photoelectric conversion layer or photoelectric conversion.
  • An auxiliary electrode provided on the surface of the layer on the second electrode side and in contact with the first electrode; a photoelectric conversion layer, the auxiliary electrode, and a carrier transporting material in contact with the second electrode; Including material.
  • the coating material preferably contains an organic substance.
  • the metal is preferably titanium.
  • the coating material preferably has a laminated structure of a metal oxide and an organic substance.
  • the film thickness of the photoelectric conversion layer is preferably 8 ⁇ m or less.
  • the dye-sensitized solar cell of the present invention preferably has a structure in which two or more photoelectric conversion layers and auxiliary electrodes are alternately laminated.
  • the coating material preferably has a laminated structure of a metal oxide and an organic substance constituting the auxiliary electrode.
  • the film thickness of the photoelectric conversion layer is preferably 8 ⁇ m or less. It is preferable that the photoelectric conversion layer and the auxiliary electrode have a structure in which they are alternately stacked.
  • a dye-sensitized solar cell module of the present invention is a module in which a plurality of the above-described dye-sensitized solar cells are connected, and the first electrode of one dye-sensitized solar cell of the adjacent dye-sensitized solar cells and the other The second electrode of the dye-sensitized solar cell is connected in series.
  • a dye-sensitized solar cell module according to the present invention is obtained by connecting a plurality of the above-described dye-sensitized solar cells, the auxiliary electrode of one dye-sensitized solar cell of the adjacent dye-sensitized solar cell, and the other dye The second electrode of the sensitized solar cell is connected in series.
  • a method for manufacturing the above dye-sensitized solar cell module wherein an auxiliary electrode of one dye-sensitized solar cell of adjacent dye-sensitized solar cells and a second electrode of the other dye-sensitized solar cell are connected in series And a step of forming a coating material on the surface of the auxiliary electrode in this order.
  • the present invention it is possible to effectively improve the FF, the short-circuit current value, and the open-circuit voltage value, and provide a dye-sensitized solar cell and a dye-sensitized solar cell module with high conversion efficiency.
  • FIG. 1 is a top view of the dye-sensitized solar cell module disclosed in Patent Document 2 and (b) is a cross-sectional view when the dye-sensitized solar cell module of (a) is cut along AA. is there.
  • (A) is typical sectional drawing of the dye-sensitized solar cell shown by patent document 3
  • (b) is a schematic diagram of another form of the dye-sensitized solar cell shown by patent document 3.
  • FIG. 1 is a cross-sectional view schematically showing an example of the structure of the dye-sensitized solar cell of the present invention.
  • the dye-sensitized solar cell 100 of the present embodiment is obtained by fixing a support body 1 and a cover body 7 with a sealing material 8, and is formed on the support body 1.
  • Two electrodes 9, a carrier transport material between the support 1 and the cover body 7, the photoelectric conversion layer 3, the auxiliary electrode 4, and the second electrode 9 are in contact with the carrier transport material 6, and the auxiliary electrode 4 is Contains two or more materials.
  • the auxiliary electrode 4 includes two or more kinds of materials, the leakage current from the auxiliary electrode 4 can be reduced, the reduction in the open-circuit voltage can be reduced, and the conversion efficiency can be improved.
  • each part which comprises the dye-sensitized solar cell 100 is demonstrated.
  • At least the portion of the support 1 that becomes the light receiving surface is made of a light transmissive material.
  • any material can be used as long as it is a material that substantially transmits light having a wavelength that has an effective sensitivity to the dye described later, and is not necessarily transparent to light in all wavelength regions.
  • the thickness of the support 1 is preferably about 0.2 to 5 mm.
  • the material constituting the support 1 is not particularly limited as long as it is generally a material that can be used for solar cells.
  • glass substrates such as soda glass, fused quartz glass, and crystal quartz glass
  • flexible films A heat-resistant resin plate such as can be used.
  • flexible films include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA), polyether imide (PEI), phenoxy resin, Examples include Teflon (registered trademark).
  • the support 1 When another member is formed on the support 1 with heating, that is, for example, when a photoelectric conversion layer made of a porous semiconductor is formed on the support 1 with heating at about 250 ° C., the support 1 It is particularly preferable to use Teflon (registered trademark) having heat resistance of 250 ° C. or higher as a material constituting the material.
  • Teflon registered trademark
  • the support body 1 can be utilized as a base
  • the first electrode 2 has conductivity and is made of a light transmissive material.
  • any material can be used as long as it can substantially transmit light having a wavelength having an effective sensitivity to the dye described later, and it is not necessarily required to be transparent to light in all wavelength regions.
  • the material constituting the first electrode 2 include indium tin composite oxide (ITO), tin oxide (SnO 2 ), tin oxide doped with fluorine (FTO), and zinc oxide (ZnO).
  • ITO indium tin composite oxide
  • SnO 2 tin oxide
  • FTO tin oxide doped with fluorine
  • ZnO zinc oxide
  • Metals that are not corrosive to the electrolytic solution such as titanium, nickel, and tantalum, can also be used.
  • the first electrode 2 can be formed on the support 1 by a known method such as a sputtering method or a spray method.
  • the film thickness of the first electrode 2 is preferably about 0.02 to 5 ⁇ m, and the film resistance is preferably as low as possible, more preferably 40 ⁇ / sq or less.
  • soda-lime float glass When using soda-lime float glass as the support 1, it is particularly preferable to use a soda-lime float glass formed on the support 1 as the first electrode 2, and a commercially available support 1 with the first electrode 2 is used. May be.
  • the photoelectric conversion layer 3 is made of a porous semiconductor that has adsorbed a dye. Below, the porous semiconductor and pigment
  • the kind of the porous semiconductor constituting the photoelectric conversion layer 3 is not particularly limited as long as it is generally used for a photoelectric conversion material.
  • titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide are used.
  • Semiconductors such as tungsten oxide, barium titanate, strontium titanate, cadmium sulfide, lead sulfide, zinc sulfide, indium phosphide, copper-indium sulfide (CuInS 2 ), CuAlO 2 , SrCu 2 O 2 and combinations thereof Can be used.
  • Titanium oxides suitably used for porous semiconductors include various narrowly defined titanium oxides such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous titanium oxide. These may be used alone or in combination.
  • the two types of crystalline titanium oxide, anatase type and rutile type can be in any form depending on the production method and thermal history, but the porous semiconductor preferably has a high content of anatase type titanium oxide, 80 More preferably, it contains at least% anatase-type titanium oxide.
  • the porous semiconductor may be formed of either a single crystal or a polycrystal, but is preferably a polycrystal from the viewpoints of stability, ease of crystal growth, manufacturing cost, and the like.
  • the porous semiconductor is preferably composed of nanoscale to microscale semiconductor fine particles, and more preferably composed of titanium oxide. Such fine particles of titanium oxide can be produced by a known method such as a gas phase method or a liquid phase method (hydrothermal synthesis method, sulfuric acid method).
  • a porous semiconductor may be formed by high-temperature hydrolysis of a chloride developed by Degussa.
  • semiconductor compounds having the same composition may be used, or two or more kinds of semiconductor compounds having different compositions may be mixed and used.
  • particle size of the semiconductor fine particles those having an average particle size of about 100 to 500 nm may be used, those having an average particle size of about 5 nm to 50 nm may be used, or these semiconductor fine particles may be mixed. You may use what you did.
  • Semiconductor fine particles having a particle size of about 100 to 500 nm scatter incident light and contribute to an improvement in light capture rate.
  • Semiconductor fine particles having an average particle size of about 5 nm to 50 nm can increase the adsorption point by increasing the adsorption point. It is thought that it contributes to the improvement.
  • the average particle size of the semiconductor fine particles having a small particle size is 10 times or more the average particle size of the semiconductor fine particles having a large particle size. It is preferable.
  • two or more kinds of semiconductor fine particles are mixed, it is effective to use a semiconductor compound having a strong adsorption action as a semiconductor fine particle having a small particle size.
  • the porous semiconductor preferably has a large surface area, for example, about 10 to 200 m 2 / g.
  • FIG. 5 is a graph showing the relationship between the thickness of the porous semiconductor and the short-circuit current when the auxiliary electrode is formed on the porous semiconductor made of titanium oxide. From the results shown in FIG. 5, it is clear that the short-circuit current value increases when the thickness of the porous semiconductor is 8 ⁇ m or less. This is presumably because the electrons collected by the first electrode due to the resistance of the porous semiconductor can be effectively carried out by installing the auxiliary electrode. From the above results, it is derived that the porous semiconductor preferably has a film thickness of 8 ⁇ m or less.
  • each of the porous semiconductor and the auxiliary electrode is preferable to stack each of the porous semiconductor and the auxiliary electrode as one unit. Thereby, the electric current value of a dye-sensitized solar cell can be improved.
  • a transparent oxide semiconductor such as ITO
  • ITO transparent oxide semiconductor
  • the dye adsorbed on the porous semiconductor functions as a photosensitizer.
  • a dye molecule having an interlock group such as a carboxyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, an ester group, a mercapto group, or a phosphonyl group is preferable.
  • the interlock group is generally present when the dye is fixed to the porous semiconductor, and provides an electrical bond that facilitates the movement of electrons between the excited state dye and the semiconductor conduction band. To do.
  • various organic dyes having absorption in the visible light region and infrared light region, metal complex dyes and the like can be used, and one or more of these dyes can be used. May be used in combination.
  • organic dyes examples include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, Examples include perylene dyes, indigo dyes, and naphthalocyanine dyes.
  • the extinction coefficient of such an organic dye is generally larger than the extinction coefficient of a metal complex dye described later.
  • the above-mentioned metal complex dye is one in which a transition metal is coordinated to a metal atom.
  • metal complex dyes include porphyrin dyes, phthalocyanine dyes, naphthalocyanine dyes, ruthenium dyes, and the like.
  • metal atoms constituting such a metal complex dye Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, Rh, etc. can be mentioned.
  • phthalocyanine dyes and ruthenium dyes in which a metal is coordinated are preferable, and ruthenium metal complex dyes are particularly preferable.
  • ruthenium-based metal complex dyes represented by the following formulas (1) to (3) are preferable.
  • examples of commercially available ruthenium-based metal complex dyes include trade name Ruthenium 535 dye, Ruthenium 535-bis TBA dye, Ruthenium 620-1H3TBA dye manufactured by Solaronix.
  • the auxiliary electrode 4 is provided together with the first electrode 2 in order to efficiently take out electrons from the photoelectric conversion layer 3.
  • Such an auxiliary electrode 4 includes two or more kinds of materials.
  • the auxiliary electrode 4 preferably has a coating material 5 on at least a part of its surface.
  • the auxiliary electrode 4 is not necessarily required to have optical transparency as long as it has conductivity.
  • ITO indium tin composite oxide
  • SnO 2 tin oxide
  • tin oxide In addition to fluorine doped (FTO), zinc oxide (ZnO), etc., metals that do not corrode to the electrolyte, such as titanium, nickel, and tantalum, can also be used.
  • Such an auxiliary electrode 4 can be formed on the photoelectric conversion layer 3 by a known method such as sputtering or spraying.
  • the auxiliary electrode 4 preferably has a film thickness of about 0.02 ⁇ m to 5 ⁇ m, and the lower the film resistance, the more preferably 40 ⁇ / sq or less.
  • the coating material 5 is preferably provided on at least a part of the surface of the auxiliary electrode 4 in order to reduce the leakage current from the auxiliary electrode 4 to the carrier transport material.
  • a coating material 5 may contain a metal oxide.
  • the metal oxide include titanium oxide, nickel oxide, tungsten oxide, tin oxide, and zinc oxide.
  • the auxiliary electrode 4 contains a metal such as titanium as a main component, it is preferably a metal oxide constituting the auxiliary electrode 4. Since such a metal oxide can be formed by oxidizing the auxiliary electrode 4, the manufacturing method is simple and the generation of leakage current can be effectively reduced.
  • the coating material 5 may be made of an organic material in addition to the above oxide. Examples of organic substances include deoxycholic acid, chenodeoxycholic acid, taurodeoxycholic acid, and the like.
  • the thickness of the coating material 5 is preferably about 10 to 120 nm.
  • the thickness of 10 nm or more is preferable because the leakage current from the auxiliary electrode 4 can be sufficiently reduced. If the thickness is less than 120 nm, the coating material 5 can be formed in a short time and contact with the photoelectric conversion layer. It is preferable because an oxide is hardly formed at the interface and electrons can be efficiently collected from the photoelectric conversion layer 3.
  • the coating material 5 consists of organic substance, it is preferable that the thickness of the coating material 5 is 1 molecule or more. This is because the organic substance can sufficiently reduce the leakage current with a thickness of about one molecule.
  • the coating material 5 or the auxiliary electrode 4 has a dense film-like structure
  • Such small holes can be formed by subjecting the auxiliary electrode 4 or the coating material 5 to physical contact or laser processing.
  • the size of the small holes is preferably about 0.1 to 100 ⁇ m, more preferably about 1 to 50 ⁇ m.
  • the interval between the small holes is preferably about 1 to 200 ⁇ m, and more preferably about 10 to 300 ⁇ m.
  • the stripe-shaped openings are preferably spaced at an interval of about 1 ⁇ m to 200 ⁇ m, more preferably at an interval of about 10 ⁇ m to 300 ⁇ m.
  • the carrier transport material 6 is filled in the support body 1 including the first electrode 2, the cover body 7 including the second electrode 9, the region surrounded by the sealing material 8, and the photoelectric conversion layer 3. ing.
  • the dye-sensitized solar cell of the present invention is not limited to that shown in FIG. 1, and may have the structure of the dye-sensitized solar cell shown in FIG.
  • the carrier transport material includes the support 1, the cover 7 and the sealing member provided with the first electrode 2, as in the dye-sensitized solar cell shown in FIG. The region surrounded by the material 8, the photoelectric conversion layer 3, and the porous insulating layer 10 are filled.
  • Such a carrier transport material 6 is composed of a conductive material capable of transporting ions.
  • a suitable material a liquid electrolyte, a solid electrolyte, a gel electrolyte, a molten salt gel electrolyte, or the like can be used.
  • the liquid electrolyte is not particularly limited as long as it is a liquid substance containing redox species, and is generally not limited as long as it is generally used in the field of solar cells. Those composed of a reducing species and a molten salt capable of dissolving the same, and those composed of a redox species, a solvent capable of dissolving the same and a molten salt can be used.
  • Examples of the redox species include I ⁇ / I 3 ⁇ series, Br 2 ⁇ / Br 3 ⁇ series, Fe 2 + / Fe 3+ series, and quinone / hydroquinone series.
  • a combination of metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI 2 ) and iodine (I 2 ), tetraethylammonium iodide (TEAI), Tetraalkylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), combinations of tetraalkylammonium salts such as tetrahexylammonium iodide (THAI) and iodine, and lithium bromide (LiBr), sodium bromide (NaBr) ), potassium bromide (KBr), calcium bromide (C
  • examples of the solvent for the redox species include carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol, water, and aprotic polar substances. Among these, carbonate compounds and nitrile compounds are particularly preferable. Two or more of these solvents can be used in combination.
  • the solid electrolyte is a conductive material that can transport electrons, holes, and ions, and can be used as an electrolyte for a solar cell and has no fluidity.
  • hole transport materials such as polycarbazole, electron transport materials such as tetranitrofluororenone, conductive polymers such as polyroll, polymer electrolytes obtained by solidifying liquid electrolytes with polymer compounds, copper iodide, thiocyanate
  • Examples thereof include a p-type semiconductor such as copper acid, and an electrolyte obtained by solidifying a liquid electrolyte containing a molten salt with fine particles.
  • Gel electrolyte usually consists of electrolyte and gelling agent.
  • gelling agents include polymer gelation such as crosslinked polyacrylic resin derivatives, crosslinked polyacrylonitrile derivatives, polyalkylene oxide derivatives, silicone resins, and polymers having a nitrogen-containing heterocyclic quaternary compound salt structure in the side chain. Agents and the like.
  • the molten salt gel electrolyte is usually composed of the gel electrolyte as described above and a room temperature molten salt.
  • the room temperature molten salt include nitrogen-containing heterocyclic quaternary ammonium salt compounds such as pyridinium salts and imidazolium salts.
  • Additives may be added to the above electrolyte as necessary.
  • Additives include nitrogen-containing aromatic compounds such as t-butylpyridine (TBP), dimethylpropylimidazole iodide (DMPII), methylpropylimidazole iodide (MPII), ethylmethylimidazole iodide (EMII), ethylimidazoleioio
  • TBP t-butylpyridine
  • DMPII dimethylpropylimidazole iodide
  • MPII methylpropylimidazole iodide
  • EMII ethylmethylimidazole iodide
  • ethylimidazoleioioio examples thereof include imidazole salts such as dye (EII) and hexylmethylimidazole iodide (HMII).
  • the electrolyte concentration in the electrolyte is preferably in the range of 0.001 mol / L to 1.5 mol / L, and more preferably in the range of 0.01 mol / L to 0.7 mol / L.
  • the cover body 7 becomes a light receiving surface, incident light reaches the photoelectric conversion layer 3 through the electrolytic solution, and carriers are excited. For this reason, the performance of the solar cell may be lowered depending on the electrolyte concentration. Therefore, it is preferable to set the electrolyte concentration in consideration of this point.
  • the second electrode 9 is not particularly limited as long as it is conductive.
  • the second electrode 9 for example, an n-type or p-type semiconductor, a metal such as gold, platinum, silver, copper, aluminum, indium, titanium, tantalum, or tungsten, or SnO 2 , ITO, CuI, or ZnO is used. Can do.
  • the second electrode 9 is the same as the support 1 in which the conductive layer is formed on the surface of the insulating substrate made of glass, plastic, transparent polymer sheet or the like, that is, the first electrode 2 is formed. Can be used.
  • a catalyst layer may be formed on the surface of the second electrode 9.
  • the catalyst layer (not shown) is preferably provided in contact with the second electrode 9.
  • a catalyst layer is not particularly limited as long as it can transfer electrons on its surface, and any material can be used, for example, noble metal materials such as platinum and palladium, carbon black, ketjen black, and carbon nanotubes. And carbon-based materials such as fullerene.
  • the dye-sensitized solar cell of the present embodiment is not limited to the form shown in FIG. 1 and may have a structure shown in FIG. 2, for example.
  • the second electrode 9 may be formed on the porous insulating layer 10.
  • the following cover body 7 is installed on the second electrode 9 and a carrier transport material is injected.
  • the porous insulating layer which comprises the dye-sensitized solar cell of FIG. 2 is demonstrated.
  • the porous insulating layer 10 is provided to prevent the auxiliary electrode 4 and the second electrode 9 from conducting.
  • the material constituting the porous insulating layer 10 include silicon oxide such as niobium oxide, zirconium oxide, silica glass, and soda glass, aluminum oxide, and barium titanate. One or two of these materials are used. More than one species can be selectively used.
  • the material used for the porous insulating layer 10 is preferably in the form of particles, and the average particle size thereof is more preferably 5 to 500 nm, still more preferably 10 to 300 nm. Further, titanium oxide or rutile type titanium oxide having a particle size of 100 nm to 500 nm can be suitably used.
  • a cover body 7 that can hold the carrier transporting material 6 inside and can prevent intrusion of water or the like from the outside is used.
  • a cover body 7 serves as a light receiving surface, the same light transmittance as that of the support body 1 is required, and therefore the same material as that of the support body 1 is used.
  • the cover body 7 is preferably made of tempered glass or the like.
  • the cover body 7 (including the case where the catalyst layer and the second electrode are formed on the surface thereof) is not in contact with the photoelectric conversion layer 3 formed on the support 1. Thereby, a sufficient amount of the carrier transport material 6 can be held inside the photoelectric conversion element.
  • a cover body 7 preferably includes an injection port for injecting the carrier transport material. The carrier transport material is injected from such an injection port using a vacuum injection method or a vacuum impregnation method.
  • the cover body 7 and the photoelectric conversion layer 3 formed on the support body 1 are not in contact, the injection speed when the carrier transport material is injected from the injection port can be increased. For this reason, the manufacturing tact of a photoelectric conversion element and a photoelectric conversion element module can be improved.
  • the sealing material 8 is provided to bond the support 1 and the cover 7 together.
  • a sealing material 8 is preferably made of a silicone resin, an epoxy resin, a polyisobutylene-based resin, a hot-melt resin, a glass-based material, or the like, and may be a laminated structure using two or more of these.
  • Examples of the material constituting the sealing material 8 include a model manufactured by Three Bond, model number: 31X-101, a model manufactured by Three Bond, model number: 31X-088, and a commercially available epoxy resin.
  • the sealing material 8 is formed using a silicone resin, an epoxy resin, or a glass frit, it is preferably formed using a dispenser.
  • a hot melt resin a sheet-like material is used. It can be formed by drilling a patterned hole in the hot melt resin.
  • FIG. 3 is a cross-sectional view schematically showing an example of the dye-sensitized solar cell module of the present embodiment.
  • the dye-sensitized solar cell module 200 of the present embodiment includes a first electrode 2 formed on a support 1, a photoelectric conversion layer 3 formed on the first electrode, and a photoelectric
  • the auxiliary electrode 4 formed on the conversion layer 3, the coating material 5 positioned on the surface of the auxiliary electrode 4, the porous insulating layer 10 formed on the coating material 5, and the porous insulating layer 10.
  • an inter-cell insulating portion 11 is formed on the first electrode 2, and the dye-sensitized solar cell is partitioned by the inter-cell insulating portion 11.
  • the inter-cell insulating portion 11 will be described later.
  • the sealing material 8 is installed on the insulation part 11 between cells, the cover body 7 is distribute
  • a carrier transport material 6 is injected between the first electrode 2 and the cover body 7 from an injection port formed in the cover body 7.
  • the carrier transport material 6 is also included in the porous insulating layer 10 and the photoelectric conversion layer 3.
  • one dye-sensitized solar cell of adjacent dye-sensitized solar cells is used. It is preferable to electrically connect the first electrode 2 and the second electrode 9 of the other dye-sensitized solar cell in series. By connecting in this way, each dye-sensitized solar cell is connected in series, and the output per unit area of a dye-sensitized solar cell module can be enlarged.
  • FIG. 4 is a cross-sectional view schematically showing another example of the dye-sensitized solar cell module of the present embodiment.
  • the dye-sensitized solar cell module of the present embodiment may connect adjacent dye-sensitized solar cells in series. That is, the dye-sensitized solar cell module shown in FIG. 4 includes the auxiliary electrode 4 of one dye-sensitized solar cell of the adjacent dye-sensitized solar cell and the second electrode 9 of the other dye-sensitized solar cell. They are connected in series. By connecting in this way, the non-power generation part in a light-receiving surface can be reduced, and the output per unit area of a dye-sensitized solar cell module can be enlarged.
  • the inter-cell insulating portion 11 is provided to electrically insulate between the dye-sensitized solar cells.
  • Such an inter-cell insulating portion 11 needs to be a material that can electrically insulate the dye-sensitized solar cells from each other, and it is preferable to use a material that can be easily formed in a desired shape on the support 1.
  • an ultraviolet curable resin, a thermosetting resin, or the like can be used as a material constituting such an inter-cell insulating portion 11, a silicone resin, an epoxy resin, a polyisobutylene resin, a hot melt resin, a glass material. In addition, two or more of these may be used to form a laminated structure.
  • the photoelectric conversion layer 3 is formed after the inter-cell insulating portion 11 is formed, it is necessary to have heat resistance with respect to the temperature when the photoelectric conversion layer 3 is formed. Further, when the support 1 is used as a light receiving surface, the inter-cell insulating portion 11 is also irradiated with ultraviolet rays, and therefore, it is preferable to use a material having light resistance to ultraviolet rays. For this reason, it is preferable to use a glass-based material.
  • the glass-based material used for the inter-cell insulating portion 11 for example, a commercially available glass paste or glass frit can be used. In particular, in consideration of reactivity with the carrier transport material and environmental problems, a lead-free glass-based material is preferable. Furthermore, when forming the inter-cell insulating part 11 on the support 1 made of a glass material, it is preferable to form it at a firing temperature of 550 ° C. or less. For example, a bismuth glass paste or a tin phosphate glass paste is suitably used. Can be used.
  • a scribe line 12 is formed by patterning a predetermined location of the first electrode 2 using a laser scribing method on the first electrode 2 formed on the support 1.
  • the inter-cell insulating portion 11 is formed on the scribe line 12 formed as described above.
  • the inter-cell insulating portion 11 is formed so as to divide the photoelectric conversion layer 3 to be formed later.
  • the formation method of the inter-cell insulating part 11 is not particularly limited.
  • a dispenser can be used.
  • the insulation part 11 between cells using hot-melt resin it can form by making the hole patterned in the sheet-like hot-melt resin.
  • a porous semiconductor constituting the photoelectric conversion layer 3 is formed on the support 1.
  • the method for forming the porous semiconductor is not particularly limited, and a known method can be used. That is, for example, a suspension in which semiconductor fine particles are suspended in a suitable solvent is applied to a predetermined place using a known method such as a doctor blade method, a squeegee method, a spin coating method, or a screen printing method, followed by drying and baking. It is formed by performing at least one.
  • the viscosity of the suspension is adjusted to be low and applied to the region divided by the inter-cell insulating portion 11 from a dispenser or the like. Is preferred. Thereby, it spreads to the edge part of the said area
  • the solvent used in the suspension examples include glyme solvents such as ethylene glycol monomethyl ether, alcohols such as isopropyl alcohol, alcohol-based mixed solvents such as isopropyl alcohol / toluene, and water.
  • glyme solvents such as ethylene glycol monomethyl ether
  • alcohols such as isopropyl alcohol
  • alcohol-based mixed solvents such as isopropyl alcohol / toluene
  • water water.
  • a commercially available titanium oxide paste for example, Solaronix, Ti-nanoxide, T, D, T / SP, D / SP
  • Ti-nanoxide for example, Solaronix, Ti-nanoxide, T, D, T / SP, D / SP
  • a porous semiconductor is formed on the support 1 by applying the suspension thus obtained onto the first electrode 2 and then performing at least one of drying and baking.
  • known methods such as a doctor blade method, a squeegee method, a spin coating method, and a screen printing method can be used.
  • the conditions (temperature, time, atmosphere, etc.) necessary for drying and firing the porous semiconductor may be set as appropriate according to the type of semiconductor fine particles.
  • the conditions (temperature, time, atmosphere, etc.) necessary for drying and firing the porous semiconductor may be set as appropriate according to the type of semiconductor fine particles.
  • the porous semiconductor may be a laminate of a plurality of layers.
  • the porous semiconductor After forming the porous semiconductor in this way, it is preferable to perform post-treatment in order to improve electrical connection between the semiconductor fine particles.
  • the porous semiconductor is made of titanium oxide
  • the performance of the porous semiconductor can be improved by post-treatment with an aqueous titanium tetrachloride solution.
  • the surface area of the porous semiconductor may be increased, or the defect level on the semiconductor fine particles may be reduced.
  • the auxiliary electrode 4 is formed on the porous semiconductor produced above (that is, the photoelectric conversion layer 3 before dye adsorption). One end of the auxiliary electrode 4 is formed up to the end of the porous semiconductor in order to contact the first electrode 2.
  • the method for forming the auxiliary electrode 4 is not particularly limited, and for example, a known method such as a sputtering method or a spray method can be used.
  • the coating material 5 is formed on the surface of the auxiliary electrode 4 produced as described above.
  • the coating material 5 may be formed by oxidizing a metal constituting the auxiliary electrode, or may be formed by applying an organic substance. That is, the coating material 5 is located on the outermost surface of the auxiliary electrode.
  • the auxiliary electrode 4 is baked in oxygen, whereby the surface of the auxiliary electrode 4 is oxidized to form the coating material 5.
  • the auxiliary electrode 4 of one dye-sensitized solar cell of adjacent dye-sensitized solar cells, and the other dye-sensitized solar cell of Adjacent dye-sensitized solar cells are connected in series by contacting the second electrode 9.
  • a porous insulating layer 10 is formed on the porous semiconductor in which the auxiliary electrode 4 is formed (that is, the photoelectric conversion layer 3 before dye adsorption).
  • a porous insulating layer 10 can be formed using a method similar to that of the above-described porous semiconductor. That is, the above-mentioned fine particle insulator is dispersed in a suitable solvent, and a polymer compound such as ethyl cellulose and polyethylene glycol (PEG) is further mixed to prepare a paste. The paste thus obtained is applied onto the auxiliary electrode 4, and at least one of drying and baking is performed. Thereby, the porous insulating layer 10 can be formed on the auxiliary electrode 4.
  • a second electrode 9 is formed on the porous insulating layer 10.
  • a method similar to the method of forming the auxiliary electrode 4 can be used.
  • the second electrode 9 has a dense film structure, a small hole may be formed in the second electrode 9.
  • each dye-sensitized solar cell is electrically connected in series by connecting the second electrode 9 and the first electrode 2.
  • the dye-sensitized solar cell module shown in FIG. 4 the dye-sensitized solar cells are electrically connected in series by connecting the second electrode 9 and the auxiliary electrode 4.
  • the photoelectric converting layer 3 is produced by making a porous semiconductor adsorb
  • the method for adsorbing the dye is not particularly limited, and for example, a method of immersing the porous semiconductor in the above-described dye adsorption solution can be used. At this time, the dye adsorbing solution may be heated in order to penetrate the dye adsorbing solution to the depths of the micropores in the porous semiconductor.
  • the solvent for dissolving the dye is not particularly limited as long as it dissolves the dye, and examples thereof include alcohol, toluene, acetonitrile, tetrahydrofuran (THF), chloroform, dimethylformamide and the like.
  • a purified one is preferably used, and two or more kinds may be mixed and used.
  • the concentration of the dye contained in the dye adsorption solution can be appropriately set according to the conditions such as the dye to be used, the type of solvent, the dye adsorption process, etc., but it is a high concentration to improve the adsorption function. For example, it is preferably 1 ⁇ 10 ⁇ 5 mol / L or more. In preparing the dye adsorption solution, heating may be performed to improve the solubility of the dye.
  • the sealing material 8 can be formed by a method similar to the method for forming the inter-cell insulating portion 11.
  • the sealing material 8 is preferably formed on the second electrode 9 in the dye-sensitized solar cell module of FIG. 3, and the second electrode 9 and the auxiliary electrode 4 are formed in the dye-sensitized solar cell module of FIG. It is preferable to be formed on the inter-cell insulating portion 11 so as to cover it.
  • the cover body 7 is disposed on the sealing material 8 and then the sealing material 8 is cured to fix the cover body 7 and the sealing material 8 together.
  • the cover body 7 is formed with an injection port, and is surrounded by the support body 1, the cover body 7, the inter-cell insulating portion 11, and the sealing material 8 by injecting the carrier transport material from the injection port.
  • the carrier transport material 6 is injected into each region to be processed.
  • the carrier transporting material 6 is injected between the support 1 and the cover body 7 from the injection port of the cover body 7. Thereby, the carrier transport material 6 is filled in the region between the support 1 and the cover body 7.
  • the carrier transport material is also filled in the holes of the photoelectric conversion layer 3 and the porous insulating layer 10.
  • the coating material 5, or the 2nd electrode 9 has a small hole, it fills also in a small diameter.
  • the dye-sensitized solar cell module 200 of this embodiment can be manufactured through the above steps.
  • the film thickness of each layer was measured using a product name: Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd., unless otherwise specified.
  • Example 1 In this example, the dye-sensitized solar cell shown in FIG. 1 was produced. Below, the preparation procedure is demonstrated concretely.
  • auxiliary electrode 4 made of titanium having a film thickness of about 500 nm is deposited at an evaporation rate of 5 mm / s using an electron beam vapor deposition device (product name: ei-5, manufactured by ULVAC, Inc.). A film was formed.
  • the titanium is evaporated by irradiating the laser beam, thereby obtaining a Scribe lines were produced at 100 ⁇ m intervals.
  • a laser scribing device manufactured by Seishin Shoji Co., Ltd.
  • a YAG laser basic wavelength: 1.06 ⁇ m
  • the auxiliary electrode 4 was baked under oxygen at 450 ° C. for 30 minutes. As a result, the surface of the auxiliary electrode 4 was oxidized, and the coating material 5 was formed on the surface of the auxiliary electrode 4.
  • the Raman spectroscopic analysis was performed on the surface of the auxiliary electrode 4, a peak of titanium oxide was confirmed. From the result of this Raman spectroscopic analysis, it became clear that the coating material 5 was formed of titanium oxide.
  • the support with a porous semiconductor produced as described above was immersed in a dye adsorption solution at 40 ° C. for 20 hours to adsorb the dye to the porous semiconductor. Thereafter, the porous semiconductor was washed with ethanol (manufactured by Aldrich Chemical Company) and dried at about 80 ° C. for about 10 minutes. In this way, the photoelectric conversion layer 3 in which the dye was adsorbed on the porous semiconductor was produced.
  • a glass similar to the glass with TCO glass used in the above support was prepared and used as the cover 7.
  • a catalyst layer made of platinum having a thickness of 30 nm is formed on the TCO surface of the cover body 7 using an electron beam vapor deposition device (product name: ei-5, manufactured by ULVAC, Inc.) at a deposition rate of 5 mm / S.
  • An electrode 9 was produced.
  • the sealing material 8 made of an ultraviolet curable resin was applied around the first electrode 2, and the cover body 7 was installed so as not to contact the second electrode 9 and the auxiliary electrode 4. And the ultraviolet curable resin was hardened by irradiating an ultraviolet-ray using the ultraviolet irradiation lamp (EFD company make, brand name: Novacure), and the cover body 7 and the support body 1 were fixed.
  • EFD company make, brand name: Novacure the ultraviolet irradiation lamp
  • an electrolyte serving as a carrier transport material was prepared. Specifically, acetonitrile as a solvent, LiI (manufactured by Aldrich Chemical Company) as a redox species has a concentration of 0.1 mol / L, I 2 (manufactured by Tokyo Chemical Industry Co., Ltd.) has a concentration of 0.01 mol / L, and As additives, t-butylpyridine (TBP, manufactured by Aldrich Chemical Company) was dissolved to a concentration of 0.5 mol / L, and dimethylpropylimidazole iodide (DMPII, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was dissolved to a concentration of 0.6 mol / L. To prepare an electrolyte.
  • LiI manufactured by Aldrich Chemical Company
  • I 2 manufactured by Tokyo Chemical Industry Co., Ltd.
  • TBP t-butylpyridine
  • DMPII dimethylpropylimidazole iod
  • the dye-sensitized solar cell of this example was produced by the same method as in Example 1 except that three layers of porous semiconductors and auxiliary electrodes were alternately laminated. That is, the porous semiconductor (titanium oxide) of this example has a total film thickness of 18 ⁇ m, and the auxiliary electrode 4 is made of 3 ITO with a film thickness of about 600 nm in consideration of light transmittance. It was formed by laminating layers.
  • the auxiliary electrode 4 was produced using a sputtering apparatus (ULVAC DC sputtering apparatus MLH-6300 type) at a tray speed of 10 mm / min.
  • the auxiliary electrode 4 having the three-layer structure as described above was immersed in an organic solvent containing deoxycholic acid for 24 hours.
  • the organic solvent contained deoxycholic acid at a concentration of 100 mM, and ethanol was used as the solvent. Then, after the auxiliary electrode 4 was taken out from the organic solvent, ethanol was removed by evaporation at 80 ° C. for 10 minutes. Then, the dye-sensitized solar cell 100 was produced by forming the coating material 5 by the method similar to Example 1.
  • Example 3 In this example, the dye-sensitized solar cell module shown in FIG. 3 was produced. Each step will be described below.
  • TCO glass manufactured by Nippon Sheet Glass Co., Ltd.
  • the first electrode 2 made of SnO 2 was formed on the support 1
  • TCO glass having a size of 44 mm ⁇ 70 mm ⁇ thickness 1 mm was used.
  • this TCO glass is set in a laser scribing device (manufactured by Seishin Shoji Co., Ltd.) equipped with a YAG laser (fundamental wavelength: 1.06 ⁇ m), and laser light is emitted at an interval of 7.5 mm with respect to the first electrode 2.
  • a laser scribing device manufactured by Seishin Shoji Co., Ltd.
  • a YAG laser fundamental wavelength: 1.06 ⁇ m
  • a screen printing plate that can be formed so that the inter-cell insulating portions 11 are arranged at intervals of 5 mm is disposed on the scribe line 12 produced above.
  • a glass paste manufactured by Noritake Company Limited, trade name: glass paste
  • a screen printing machine Nema No. 1 mm x 50 mmx8 micrometer strip-shaped inter-cell insulation part 11.
  • a screen plate in which five openings of 5 mm ⁇ 50 mm were arranged was prepared. Then, the screen plate was set so that one of the screen plates was in contact with the inter-cell insulating portion 11, and a titanium oxide paste (manufactured by Solaronix, trade name: Ti-Nanoxide D / SP, average particle size 13 nm) was screen printed. It applied using.
  • the coating film obtained here was preliminarily dried at 80 ° C. for 20 minutes and then baked at 450 ° C. for 1 hour to form a porous semiconductor having a thickness of 7 ⁇ m made of titanium oxide.
  • auxiliary electrode 4 made of titanium having a thickness of about 500 nm was formed at an evaporation rate of 5 ⁇ / S using an electron beam evaporation device ei-5 (manufactured by ULVAC, Inc.).
  • the auxiliary electrode 4 was irradiated with laser light at intervals of 100 mm using a laser scribing device (manufactured by Seishin Shoji Co., Ltd.) equipped with a YAG laser (basic wavelength: 1.06 ⁇ m). As a result, a part of the auxiliary electrode 4 was evaporated to prepare a scribe line having a width of 50 ⁇ m.
  • zirconium oxide fine particles particles size: 100 nm, manufactured by C.I. Kasei Co., Ltd.
  • ethyl cellulose was further mixed to prepare a zirconium paste.
  • the weight ratio of the zirconium oxide fine particles, terpineol, and ethyl cellulose was 65: 30: 5.
  • a screen printing plate in which strip shapes are arranged at 1 mm intervals so that the shape after firing is 6 mm ⁇ 50 mm ⁇ 3.5 ⁇ m is prepared, and a screen printing machine (manufactured by Neurong Precision Industry Co., Ltd., model: LS-34TVA) is prepared. ) was applied onto the first electrode 2 and leveled at room temperature for 1 hour. After the leveling, the obtained coating film was pre-dried at 80 ° C. for 20 minutes, and then fired at 450 ° C. for 1 hour to form a porous insulating layer 10 made of zirconium oxide.
  • the second electrode 9 was formed on the catalyst layer. Specifically, a metal mask in which five openings of 5 mm ⁇ 50 mm are arranged is prepared, and platinum is deposited on the porous insulating layer 10 using an electron beam vapor deposition device (manufactured by ULVAC, Inc., apparatus name: ei-5). A catalyst layer (not shown) made of platinum having a thickness of about 20 nm was formed at a deposition rate of 5 ⁇ / S. Then, the 2nd electrode 9 was produced on the conditions similar to the conditions when forming a catalyst layer using the metal mask and electron beam vapor deposition device similar to the above. The second electrode 9 produced in this way was also formed in a stripe shape like the first electrode 2.
  • the support 1 with a porous semiconductor produced as described above was immersed in a dye adsorption solution at 40 ° C. for 20 hours to adsorb the dye to the porous semiconductor. Thereafter, the porous semiconductor was washed with ethanol (manufactured by Aldrich Chemical Company) and dried at about 80 ° C. for about 10 minutes.
  • ⁇ Injection of carrier transport material As an additive, acetonitrile was used as a solvent, and LiI (manufactured by Aldrich Chemical Company) as a redox species had a concentration of 0.1 mol / L, and I 2 (manufactured by Tokyo Chemical Industry Co., Ltd.) had a concentration of 0.01 mol / L.
  • t-Butylpyridine TBP, manufactured by Aldrich Chemical Company
  • DMPII dimethylpropylimidazole iodide
  • Example 4 the dye-sensitized solar cell module 200 shown in FIG. 4 was produced.
  • the method for manufacturing the dye-sensitized solar cell module of this example will be described focusing on the differences from Example 3.
  • TCO glass manufactured by Nippon Sheet Glass Co., Ltd.
  • TCO glass having a size of 34 mm ⁇ 70 mm ⁇ thickness 1 mm was used.
  • this TCO glass is set in a laser scribing device (manufactured by Seishin Shoji Co., Ltd.) equipped with a YAG laser (fundamental wavelength: 1.06 ⁇ m), and laser light is emitted at an interval of 6.5 mm with respect to the first electrode 2.
  • a laser scribing device manufactured by Seishin Shoji Co., Ltd.
  • a YAG laser fundamental wavelength: 1.06 ⁇ m
  • the inter-cell insulating portion 11, the porous semiconductor, and the auxiliary electrode 4 were formed in this order by the same method as in Example 3.
  • the auxiliary electrode 4 is different from the third embodiment in that the end of the auxiliary electrode 4 is also formed above the inter-cell insulating portion 11.
  • the porous insulating layer 10 was formed so as to be in contact with the inter-cell insulating portion 11.
  • the second electrode 9 so as to be in contact with the auxiliary electrode 4 on the inter-cell insulating portion 11 adjacent dye-sensitized solar cells were electrically connected in series. That is, the auxiliary electrode 4 of one dye-sensitized solar cell of adjacent dye-sensitized solar cells and the second electrode 9 of the other dye-sensitized solar cell were connected in series. Thereafter, the auxiliary electrode 4 was baked under oxygen at 450 ° C. for 30 minutes to form the coating material 5 on the surface of the auxiliary electrode 4. As described above, the dye-sensitized solar cell module of this example was produced.
  • Example 4 has a higher short-circuit current value than Example 3, and high photoelectric conversion efficiency can be obtained. It became clear. This is because, in Example 4, the auxiliary electrode 4 of one dye-sensitized solar cell of adjacent dye-sensitized solar cells and the second electrode 9 of the other dye-sensitized solar cell are connected in series. Conceivable.
  • the present invention can be widely used for dye-sensitized solar cells and dye-sensitized solar cell modules.

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Abstract

L'invention concerne une cellule solaire à colorant dans laquelle le facteur de remplissage, la valeur du courant de court-circuit et la valeur de la tension de circuit ouvert peuvent être améliorés efficacement ; ainsi qu'un module de cellules solaires à colorant. La cellule solaire à colorant comprend une première électrode, une seconde électrode qui est disposée de façon à faire face à la première électrode, une couche de conversion photoélectrique qui est en contact avec la première électrode, une électrode auxiliaire qui est disposée dans ou sur la surface de la couche de conversion photoélectrique du côté de la seconde électrode et qui est au contact de la première électrode, et un matériau de transport de porteurs qui est en contact avec la couche de conversion photoélectrique, l'électrode auxiliaire et la seconde électrode. La cellule solaire est caractérisée en ce que l'électrode auxiliaire comprend au moins deux matériaux.
PCT/JP2011/077613 2010-12-20 2011-11-30 Cellule solaire à colorant et module de cellules solaires à colorant, ainsi que procédés pour leur production Ceased WO2012086377A1 (fr)

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