WO2009001343A2 - Pile sèche ayant une couche de cathode frittée - Google Patents

Pile sèche ayant une couche de cathode frittée Download PDF

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Publication number
WO2009001343A2
WO2009001343A2 PCT/IL2008/000856 IL2008000856W WO2009001343A2 WO 2009001343 A2 WO2009001343 A2 WO 2009001343A2 IL 2008000856 W IL2008000856 W IL 2008000856W WO 2009001343 A2 WO2009001343 A2 WO 2009001343A2
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WO
WIPO (PCT)
Prior art keywords
particles
photovoltaic cell
conductive carbon
layer
conductive
Prior art date
Application number
PCT/IL2008/000856
Other languages
English (en)
Other versions
WO2009001343A3 (fr
Inventor
Eli Rosh Hodesh
Jonathan R. Goldstein
Barry Breen
Ilya Yakupov
Original Assignee
3Gsolar Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/IL2008/000671 external-priority patent/WO2008139479A2/fr
Application filed by 3Gsolar Ltd. filed Critical 3Gsolar Ltd.
Priority to PCT/IL2008/000933 priority Critical patent/WO2009007957A2/fr
Priority to PCT/IL2008/001168 priority patent/WO2009027977A2/fr
Priority to CN201210365063.8A priority patent/CN102969167B/zh
Priority to CN200880113787.5A priority patent/CN101842905B/zh
Publication of WO2009001343A2 publication Critical patent/WO2009001343A2/fr
Priority to AU2009250946A priority patent/AU2009250946B2/en
Publication of WO2009001343A3 publication Critical patent/WO2009001343A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage 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
    • H01G9/2022—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
    • H01G9/2027—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

Definitions

  • the present invention relates to photovoltaic dye cells for producing electricity directly from sunlight, and more particularly, to iodine-based dye cells having a sintered cathode layer.
  • the invention has particular relevance for solar cells of the dye-sensitized type (the so called DSSC or dye-sensitized solar cell) in which a high current density of operation at minimal ohmic loss is advantageous.
  • Dye-sensitized photovoltaic cells for producing electricity from sunlight have been disclosed by U.S. Patent No. 5,350,644 to Graetzel, et al.
  • U.S. Patent No. 5,350,644 which is incorporated by reference for all purposes as if fully set forth herein, teaches a photovoltaic cell having a light-transmitting, electrically conductive layer deposited on a glass plate or a transparent polymer sheet to which a series of titanium dioxide layers have been applied.
  • U.S. Patent No. 5,350,644 U.S. Patent No. 6,069,313 to Kay teaches a plurality of series-connected cell elements arranged as electrically separate, parallel, narrow elongated strips on a common transparent substrate.
  • Each element includes a light facing anode comprising nanocrystalline titania, a carbon-based counter electrode (cathode), and an intermediate electrically insulating porous layer separating the anode from the cathode.
  • the pores of the intermediate layer are at least partially filled with a liquid phase, ion-transferring electrolyte, following coating of the nanocrystalline titania with a light-sensitive dye.
  • a current collecting layer of a tin oxide based, transparent, electrically-conducting material is situated between the transparent substrate and the anode.
  • the anode and cathode of a given cell provide a direct current voltage when the anode is exposed to light, such that series assemblies of cells may readily be built up.
  • the cathode of each succeeding element is connected with the inte ⁇ nediate conducting layer of the preceding anode element, over a gap separating the respective intermediate layers of these two elements.
  • the series of cells (also known as a monolithic assembly of cells) is then sealed using an organic polymer, ensuring in particular that each individual strip cell is sealed from neighboring cells.
  • dye cells have two electrodes separated by an electrolyte, with one electrode (the photoelectrode or photoanode) facing the sun or light source.
  • Each electrode is supported on its own current collector, usually a sheet of conducting glass, which is glass coated on one side with a thin (-0.5 micrometer) transparent layer, usually based on electrically conductive tin oxide.
  • the conducting glass sheets act as transparent walls of the dye cell.
  • a transparent polymer may be used in place of glass to support the tin oxide.
  • the photoelectrode or photoanode includes a transparent porous layer about 10 micrometers thick (in contact with the tin oxide layer) based on titania, having a nanocrystalline characteristic particle size of 5-50 nm, applied by baking onto the conductive glass or conductive transparent polymer, and impregnated with a special dye.
  • the baked-on titania layer is applied in dispersion form by any of various methods: doctor-blading, rolling, spraying, painting, electrophoresis, gravure printing, slit coating, screen printing or printing.
  • the baking step giving highest cell performance is usually performed at a temperature of at least 450C, requiring the use of conducting glass rather than plastic for supporting the titania layer.
  • Other processing procedures for the titania layer are feasible, such as reduced temperature baking, or pressing, usually with some sacrifice in cell efficiency.
  • the titania is principally in contact with the tin oxide.
  • the presence of other conductors such as many metals, carbon and the like, on the photoanode, even if they are chemically inert to the electrolyte, can greatly increase recombination of charge carriers and provide a serious efficiency loss in the cell.
  • the other electrode in the cell includes a thin layer of catalyst (usually containing a few micrograms of platinum per sq. cm) on its respective sheet of tin oxide coated conductive glass or transparent plastic. If cell transparency is not required, the counter electrode can be opaque, for example, based on carbon or graphite advantageously catalyzed with trace platinum or another catalyst.
  • the electrolyte in the cell is usually an organic solvent with a dissolved redox species.
  • the electrolyte is typically acetonitrile or a higher molecular weight reduced volatility nitrile, with the redox species in early cells including dissolved iodine and potassium iodide-essentially potassium triiodide.
  • redox species in early cells including dissolved iodine and potassium iodide-essentially potassium triiodide.
  • Other solvents, salts and phases, for example ionic liquids with no vapor pressure, and even different redox species, may be used, however.
  • U.S. Patent No. 5,350,644 to Graetzel et al. discloses various dye cell chemistries, especially different dyes based on ruthenium complexes. Photons falling on the photoelectrode excite the dye (creating activated oxidized dye molecules), causing electrons to enter the conduction band of the titania and to flow (via an outer circuit having a load) to the counter electrode. There, the electrons reduce triiodide to iodide in the electrolyte, and the iodide is oxidized by the activated dye at the photoanode back to triiodide, leaving behind a deactivated dye molecule ready for the next photon.
  • U.S. Patent No. 5,350,644 discloses that such dye cells can attain a solar-to-electric conversion efficiency of 10%.
  • the cells of U.S. Patent No. 5,350,644 to Graetzel, et al. are based on two sheets of conductive glass sealed with organic adhesive at the edges (the conductive glass projects beyond the adhesive on each side, allowing for current takeoff). These cells operate at a voltage of about 700 mV and a current density of 15 mA/sq. cm under peak solar illumination, with the counter electrode being the positive pole. It is asserted therein that since the materials and preparation methods are low cost and the titania layer can be prepared in large areas, such cells could potentially provide a good route to low-cost photovoltaic cells.
  • tin oxide is only semiconductive and is difficult to bond to, such that the current takeoff is significantly limited by such a cell design to very small sized cells or strip cells with long narrow strips of active titania.
  • active strip cells of this approach have certain technical disadvantages. For example, in the cells of Kay described above, the strips of titania are disadvantageously narrow (typically 6-8 mm wide), due to the ohmic loss restriction. This results in an excessive loss of active area between cells, due to the practical width of inert materials needed for intercell sealing. In any event, adequate sealing between adjacent cells so as to effectively prevent any intercell electrolyte migration remains a serious challenge.
  • the high process temperatures required for the silver and glaze compositions adversely affect the conductivity and strength properties of the glass. Glaze materials that can be processed at lower temperatures are available, but contain toxic heavy metals such as lead, which may be attacked by the electrolyte and poison the cathode catalyst. Furthermore, protection of silver conductors by a glass layer is inadequate over time, since pinholes cannot be entirely eliminated in the glaze, especially in mass production processes. In fact, exposed silver is spontaneously corroded by the iodine in cell electrolytes, adversely reducing the iodine inventory in the cell and irreversibly attacking the dye, and a similar deterioration occurs with silver lines protected by polymer. Of course, the additional width needed for protective glaze or polymer coatings over the silver lines further reduces the cell active area.
  • a further problem in prior art dye cells and modules has been excessive surface area wasted in seals, protective layers and conducting paths on the sun-facing side of the cell or module.
  • the active current-producing area in such cases is often less than 70% of the geometric area (footprint) of the cell or module, providing a poor effective efficiency from the available area.
  • a yet further problem in prior art cells, especially if the counterelectrode is a separate element from the anode, is the relatively large spacing between anode and cathode — approaching 100 micrometers — which results in excessive ohmic loss from the electrolyte
  • U.S. Patent Application Publication No. 20050072458 to Goldstein which is incorporated by reference for all purposes as if fully set forth herein, describes a large area, broad conductive glass or conductive plastic for a dye cell.
  • the conductive glass or conductive plastic carries a set of conductors selected from materials intrinsically resistant to corrosion and to carrier recombination in the presence of the cell electrolyte, and onto this superior glass or plastic (having enhanced current collecting properties over plain conductive glass or plastic) the titania is deposited.
  • a conductive glass face is first grooved, giving a set of parallel spaced shallow grooves.
  • a wire of a metal such as titanium, molybdenum, tungsten, chromium or their alloys (inert to corrosion and to carrier recombination under the operating conditions of the cell) and electrical conductivity between the wire and the tin oxide layer on each side of the groove is achieved using a heat-curable binder paste based on an inert ceramic adhesive (such as alumina) mixed with an inert, electrically conducting filler (such as titanium nitride).
  • the paste fills the groove and overlaps on each side of the groove to make good electrical contact with the tin oxide layer there following curing.
  • the wires exit from the cell from the groove extremities at the glass edges and may be sealed in and welded to a current-collecting strip.
  • the parallel conductors are inert strips or wires of titanium, molybdenum, tungsten, chromium or their alloys bonded directly to the conducting surface of the glass by means of an inert, electrically conducting ceramic adhesive.
  • U.S. Patent Application Publication No. 20050072458 extends the use of wires in a grooved conductive glass or of strips plated on conductive glass also for use in the counter electrode (cathode) of the cell.
  • the glass plate provided with wires bonded in grooves or with plated strips on the conductive surface, is used as a base for a broad cathode in the dye cell, and the conductivity-augmented plate is covered with a catalytic layer electroactive to iodine.
  • Such a cathode although fitted with adequate conducting means for current takeoff from a large area broad cell, necessarily includes a second layer of conducting glass in the cell, with associated cost, weight and thickness penalties. Broad dye cells of at least 10-15 cm per side are made possible, however.
  • Adequate current takeoff from the cathode is achieved by incorporating metal wires, mesh or perforated sheet at least partially embedded in the carbon.
  • the titania is then coated with dye and the cell is filled with electrolyte by direct application of solutions to the porous cathode surface.
  • the cell is then sealed using polymer means or using a glass sheet with edge sealing. Close spacing of anode and cathode may be achieved.
  • a metal foil, itself catalyzed or carrying a catalyzed carbon layer is used to close off the cell sandwich and take out the current from the cell.
  • the sintered-on spacer layer may be omitted and adequate spacing off from the titania is achieved using an edge- mounted gasket or a freestanding porous separator.
  • Lowest cost cells whether of the monolithic multicell type or the large area single cell type, will advantageously employ a carbon-based cathode. If possible, such cells are devoid of precious metal catalyst additions.
  • a carbon-based cathode element may be prepared from an aqueous dispersion of carbon black and colloidal nanocrystalline titania as binder.
  • a photovoltaic cell for converting a light source into electricity, the cell including: (a) a housing adapted to enclose the photovoltaic cell, the housing including an at least partially transparent cell wall, the cell wall having an interior surface; (b) an electrolyte, disposed within the cell wall, the electrolyte containing an iodine-based redox species; (c) an at least partially transparent conductive coating disposed on the interior surface of the cell wall, within the photovoltaic cell; (d) an anode disposed on the conductive coating, the anode including: (i) a porous film adapted to make intimate contact with the redox species, the porous film including chemically bonded titanium dioxide nanoparticles, and (ii) a dye, absorbed on a surface of the porous film, the dye and the film adapted to convert photons to electrons; (e) a cathode disposed within an interior surface of the housing, the catho
  • a method of producing a photovoltaic cell for converting a light source into electricity including the steps of: (a) providing: (i) a housing adapted to enclose the photovoltaic cell, the housing including an at least partially transparent cell wall, the cell wall having an interior surface; (ii) an at least partially transparent conductive coating disposed on the interior surface of the cell wall, within the photovoltaic cell; (iii) an anode disposed on the conductive coating, the anode including a porous film adapted to make intimate contact with a redox species, the porous film including titanium dioxide nanoparticles, and (b) providing a cathode generally opposite the anode, the cathode including a sintered conductive carbon layer, the conductive carbon layer including: (i) carbon black particles; (ii) graphite powder; (iii) expanded graphite particles, and (iv) titanium dioxide particles, the titanium dioxide particles of the conductive carbon layer being chemical
  • a method of producing a photovoltaic cell for converting a light source into electricity including the steps of: (a) providing: (i) a housing adapted to enclose the photovoltaic cell, the housing including an at least partially transparent cell wall, the cell wall having an interior surface; (ii) an at least partially transparent conductive coating disposed on the interior surface of the cell wall, within the photovoltaic cell; (iii) an anode disposed on the conductive coating, the anode including a porous film adapted to make intimate contact with a redox species, the porous film including titanium dioxide nanoparticles; (b) disposing a conductive carbon paste opposite the anode, the paste including: (A) carbon black particles; (B) graphite powder; (C) expanded graphite particles, (D) at least one ceramic oxide precursor, the precursor selected from the group of precursors consisting of a titania precursor and a zirconia precursor, and (E)
  • a method of producing a photovoltaic cell for converting a light source into electricity including the steps of: (a) providing: (i) a housing adapted to enclose the photovoltaic cell, the housing including an at least partially transparent cell wall, the cell wall having an interior surface; (ii) an at least partially transparent conductive coating disposed on the interior surface of the cell wall, within the photovoltaic cell; (iii) an anode disposed on the conductive coating, the anode including a porous film adapted to make intimate contact with a redox species, the porous film including titanium dioxide nanoparticles; (b) providing a conductive carbon paste, the paste including: (A) carbon black particles; (B) graphite powder; (C) expanded graphite particles; (D) at least one ceramic oxide precursor, the precursor selected from the group of precursors consisting of a titania precursor and a zirconia precursor, and (E) a liquid vehicle, the carbon
  • the conductive carbon layer is a sintered conductive carbon layer.
  • the porous film is sintered to the conductive coating.
  • the carbon black particles, graphite powder, expanded graphite particles, and titanium dioxide particles are distributed in a substantially uniform manner within the sintered conductive carbon layer.
  • the conductive carbon layer is in a state of rigid attachment to the porous film.
  • the cell further includes: (f) a porous separator layer interdisposed between the porous film of the anode and the catalytic component of the cathode, the porous separator layer adapted to physically separate and electrically insulate between the porous film and the cathode.
  • the porous separator layer includes a spacing element that is physically distinct with respect to the porous film of the anode.
  • the porous separator layer includes a spacing element that is chemically bonded to the porous film of the anode.
  • the porous separator layer includes a spacing element that is sintered to the porous film of the anode.
  • the spacing element is selected from the group of structural elements consisting of glass fiber and microporous polymer.
  • the chemically bonded titanium dioxide nanoparticles include sintered titanium dioxide nanoparticles.
  • the conductive carbon layer is in a state of rigid attachment with respect to the porous separator layer.
  • the conductive carbon layer is chemically bonded to the porous separator layer.
  • the conductive carbon layer is sintered to the porous separator layer.
  • the cell further includes: (f) at least one metal strip or wire, electrically associated with the anode and with the conductive coating, the strip or wire having sufficient thickness to fo ⁇ n a protrusion protruding above a plane of the porous film by at least 50 micrometers.
  • the at least one metal strip or wire is bonded to the transparent conductive coating by a conductive binding material.
  • the conductive binding material includes a ceramic adhesive. According to still further features in the described preferred embodiments, the conductive binding material includes titanium nitride.
  • the at least one metal strip or wire is a plurality of wires
  • the protrusion is a plurality of protrusions.
  • the conductive carbon layer further includes: (E) zirconium oxide particles, preferably distributed in a substantially uniform manner with the carbon black particles, the graphite powder, the expanded graphite particles, and the titanium dioxide particles.
  • the carbon black and the expanded graphite have a weight ratio in a range of 1.5: 1 to 1 : 1.5.
  • the total carbon content of the conductive carbon layer includes the graphite powder, the carbon black particles, and the expanded graphite particles, and the total carbon content and the titanium dioxide particles have a weight ratio in a range of 1.2: 1 to 3.5:1.
  • the graphite powder has a weight ratio with respect to the sum of the carbon black particles and the expanded graphite particles, the weight ratio falling in a range of 1.5: 1 to 3.5: 1.
  • the graphite powder has a weight ratio with respect to a sum of the carbon black particles, the expanded graphite particles, and the zirconium oxide particles, the weight ratio falling in a range of 1.2: 1 to 3: 1.
  • the total carbon content of the conductive carbon layer includes the graphite powder, the carbon black particles, and the expanded graphite particles, and the weight ratio of the total carbon content and the zirconium oxide particles to the titanium dioxide particles falls in a range of 1.5: 1 to 4: 1.
  • the width (i.e., the narrow dimension of the face) of the conductive carbon layer is at least 5 cm.
  • the width of the conductive carbon layer is at least 8 cm.
  • the width of the conductive carbon layer is at least 10 cm. According to still further features in the described preferred embodiments, the width of the conductive carbon layer is at least 15 cm.
  • the expanded graphite particles have a long dimension of at least 15 micrometers, on average.
  • the expanded graphite particles have a long dimension of at least 25 micrometers, on average.
  • the expanded graphite particles have a long dimension of at least 40 micrometers, on average.
  • the expanded graphite particles have a long dimension of at least 60 micrometers, on average.
  • the titania particles have an average primary particle size below 50 nm.
  • the titania particles have an average primary particle size below 30 nm.
  • the method further includes, prior to providing the cathode having the sintered conductive carbon layer, (c) disposing a conductive carbon paste opposite the anode, the paste including: (i) carbon black particles; (ii) graphite powder; (iii) expanded graphite particles,
  • the disposing of the conductive carbon paste opposite the anode is performed by screenprinting the paste.
  • the method further includes the step of: (c) disposing a porous, electrically insulative separator on the anode, to electrically insulate between the anode and the cathode.
  • the method further includes the step of: (d) disposing a porous, electrically insulative separator on the anode, to electrically insulate between the anode and the cathode, wherein the disposing of the conductive carbon paste is performed directly on a surface of the porous, electrically insulative separator.
  • the ceramic oxide precursor includes a titanium or zirconium chelate.
  • the ceramic oxide precursor is a titania precursor.
  • the titania precursor includes an organic titanate.
  • the titania precursor includes a compound selected from the group of titania precursors consisting of organic titanium chelates, aqueous titanium chelates, organic titanates and ortho-titanate esters.
  • the titania precursor includes a titanium acetylacetonate.
  • the liquid vehicle includes an alcohol.
  • the sintering of the conductive carbon paste to convert the ceramic oxide precursor to sintered ceramic oxide articles is performed in an air-containing environment
  • the ceramic oxide precursor includes a fumeless precursor that reacts in the air-containing environment in a substantially non-fuming fashion.
  • the cathode includes a support matrix structurally supporting the conductive carbon layer and sintered thereto.
  • the conductive carbon layer includes: (v) zirconia particles, intimately dispersed within the conductive carbon layer.
  • the conductive carbon layer includes: (vi) zirconia particles, intimately dispersed within the conductive carbon paste.
  • the method further includes the step of: (d) disposed within the cell wall, an electrolyte, the electrolyte containing an iodine-based redox species.
  • the screenprinting of the paste is performed over a cell width of at least 5 cm, and preferably, at least 10 or at least 15 cm.
  • the sintered conductive carbon layer is produced by sintering the conductive carbon paste at a temperature above 350C.
  • the sintered conductive carbon layer is produced by sintering the conductive carbon paste at a temperature above 400C.
  • the matrix is selected from a group of matrices consisting of glass fiber mat, carbon fiber mat, zirconia felt, titania felt and carbon foam.
  • FIG. 1 is a schematic cross-sectional view of an exemplary photovoltaic cell having a biplate construction and a sintered cathode layer;
  • FIG. 2 is a schematic cross-sectional view of an exemplary embodiment of another inventive photovoltaic cell having a monolithic construction and a sintered cathode layer;
  • FIG. 3 is a schematic cross-sectional representation of a porous carbon paste layer following sintering, according to the present invention
  • FIG. 4 is a schematic cross-sectional representation of a porous carbon paste layer following sintering, according to the prior art.
  • FIG. 1 is a schematic cross-sectional view of an exemplary photovoltaic cell 600 having a biplate construction in which the anode and cathode components in the cell build are physically distinct and not bonded together.
  • the photoanode of cell 600 includes a porous nanocrystalline titania layer or film 138.
  • Porous titania layer 138 has an extremely thin layer of dye (typically a monolayer of dye) absorbed on a surface of the porous titania layer.
  • the dye and film are adapted to convert photons to electrons.
  • a photoanode support glass 30 with transparent conductor layer 32 has spaced, preferably parallel wires or strips such as wire 110 bonded in place on the surface of the conductive glass by a conducting adhesive such as an inert conducting ceramic adhesive 115.
  • Porous titania layer 138 is bonded to transparent conductor layer 32 in most of the area between adjacent wires 110. Both the titania and the conducting adhesive bonding the wires may be optionally covered by an electrically insulating layer, for example, consisting of, consisting essentially of, or including zirconia, for additional protection against short-circuiting.
  • a porous, laid-on separator 125 such as a glass fiber veil or a microporous polymer membrane, may electrically insulate the photoanode from a counterelectrode 192.
  • Counterelectrode 192 may include a plurality of strips, each strip including a conducting carbon layer 185 and catalytic carbon layer 190, which may alternatively form a single layer.
  • Conducting carbon layer 185 and/or catalytic carbon layer 190 may include an inert matrix including a porous mat, felt or foam based on glass fiber, carbon or a ceramic oxide such as zirconia or titania.
  • Porous separator 125 may be extremely thin and porous (preferably having a thickness of less than 50 micrometers in an uncompressed state), and of a material that is chemically stable in the cell (for example: polyethylene, PET, PPS, PEN, fluoropolymer or glass fiber).
  • Cathodic current collector such as collector sheet 310 may be made of, consist essentially of, or include, a metal sheet selected from the cathode metals and alloys provided hereinabove. Collector sheet 310 is adapted to firmly press against counterelectrode 192.
  • the metal sheet of collector sheet 310 can be directly catalyzed with platinum or a platinum substitute, and may be structured (by corrugation or machining, for example) with periodically spaced projecting areas (not shown) to ensure close proximity (via the porous membrane) of catalyst to titania between the wires of the photoanode.
  • counterelectrode 192 is disposed substantially opposite the titania printings, and may be of pre-designed thickness, such that there is a relatively close proximity (across the porous separator) of the catalyzed carbon layer and the titania layer between the wires after cell closure and sealing.
  • metal collector sheet 310 is hot sealed to the glass anode base-plate edges using, by way of example, an inner polymer sealing layer or seal 165 and an outer epoxy sealing layer or seal 170.
  • cell 600 is filled with electrolyte, one possibility being adding electrolyte to the cell via fill holes and later sealing off the fill holes with polymer.
  • Current take-off from collector sheet 310 out of the cell may be enabled by a projecting strip or a welded-on element.
  • photoanode support glass 30 and collector sheet 310 form a housing substantially enclosing cell 600.
  • FIG. 2 is a schematic cross-sectional view of an exemplary embodiment of another inventive photovoltaic cell 800 having a cathodic current collector including, or consisting essentially of, a conductive, chemically inert mesh or foil 195, preferably disposed above, and physically contacting, counterelectrode 320.
  • counterelectrode 320 is sintered onto electrically insulating layer 220, typically zirconia. Electrically insulating layer 220 typically has a relatively uniform thickness in a range of 2-15 micrometers.
  • the catalytic layer is disposed towards electrically insulating layer 220.
  • a photoanode support glass 30 coated with substantially transparent conductor layer 32 may have spaced, preferably parallel wires 110 bonded in place on the surface of the conductive glass by inert conducting ceramic adhesive 115. Between wires and at the cell edges is a sintered nanoporous titania layer 138, typically 10-15 micrometers thick, which is covered with electrically insulating layer 220, e.g., including zirconia.
  • the wires may typically have a diameter of at least 100 micrometers, and the combined height of the titania and zirconia layers is typically below about 30 micrometers, the wires project substantially above the titania layer and may be covered also by an electrically insulating layer 225, for example including zirconia, to avoid short circuiting to counterelectrode 320.
  • the sealing arrangement of cell 800 may be substantially identical to the arrangement provided in Figure 1 and described hereinabove.
  • cell 800 may be sealed on top by a sheet such as ordinary, inexpensive glass sheet 190, disposed above mesh or foil 195, and may also be adapted to provide the requisite structural support for mesh or foil 195 as well as the requisite compressive force against mesh or foil 195.
  • Conductive mesh or foil 195 may pass sealably out through seals 165, 170 of photovoltaic cell 800.
  • Conductive mesh or foil 195 may include, or consist essentially of, a metal mesh or foil.
  • Conductive mesh or foil 195 may include, or consist essentially of, a graphite mesh or foil, or a carbon mesh or foil.
  • Composite cathodic current collectors including graphite and/or carbon and/or metal meshes or foils may also be practical. It may be particularly advantageous to use a graphite or carbon foil to cover the central area of photovoltaic cell 800, and to boost current takeoff near the edges of cell 800 by electrically connecting the edges of the carbon or graphite foil to a metal mesh and/or foil disposed near a perimeter of cell 800 and passing sealably out through seals 165, 170 of cell 800.
  • the prior art does not provide carbon pastes that can be successfully applied by screenprinting to large area cells of the monolithic or single cell design with cell areas significantly above 10 sq. cm. Screenprinting, rather than doctor blading, is the application method of choice for industrial production of broad, large-area dye cells.
  • Screenprinting rather than doctor blading, is the application method of choice for industrial production of broad, large-area dye cells.
  • water based formulations are attempted for screenprinting of the carbon for dye cells there emerge several obstacles.
  • the prior art water-based carbon pastes tend to be quick drying and can clog the screens used in production scale screenprinting. Certain additives may ease this situation somewhat.
  • the insufficient mechanical strength is principally a result of the incorporation of particulate titania intrinsically as the binder, since this material does not sinter strongly enough to the carbon materials in the paste nor to the substrate beneath.
  • a titania precursor is used (instead of titania powder) which, during the usual sintering in air, provides titania centers in situ throughout the layer and forms stronger bonds with the carbon materials used and, in some preferred embodiments, with the substrate beneath (usually a spacer layer of porous zirconia).
  • titania precursors that oxidize acceptably to titania on sintering in air, for example the titanium alkoxides, appear to be unsuitable for paste formulation, because they fume strongly in air and are difficult to work with.
  • a non- limiting example of a benign, suitable precursor is the family of organic titanates supplied by DuPont under the trade name TyzorTM.
  • organic titanates are available in the form of organic chelates, aqueous chelates, and ortho-titanate esters. These precursors contain about 15 wt% of titania equivalent, and oxidation to titania is usually complete on heating in air at above 300C for 30 minutes.
  • TyzorTM grade AA-75 which is based on titanium acetylacetonates in an alcoholic solvent.
  • other grades of TyzorTM are also applicable.
  • the parallel zirconium chelates may also be used (which sinter in situ to zirconia), but these are more expensive than their titanium analogs.
  • Prior art carbon pastes for the dye cell cathode normally consist of high surface area conductive grade carbon black (at least 150 sq. meter per gram) with typical particle size of up to 50 nanometers, together with graphite powder having an average particle diameter of several micrometers as the main additive for boosting conductivity.
  • Expanded graphite which is graphite that has been chemically exfoliated to give large, flat, anisometric, two-dimensional platelets of particle size selectable from about 20-100 micrometers and having a surface area of about 10-30 sq. meters per gram, is a much more effective conductivity booster and also provides improved anchoring and mechanical stability for the layer.
  • the carbon, graphite and titania precursor components are conveniently dispersed in a printing vehicle such as terpineol or ethyl hexanol.
  • the paste may be made more viscous and printable, giving a print with improved green strength, by the incorporation into the terpineol of a heat fugitive thickening agent such as ethyl cellulose.
  • Additional conducting filler powders that are chemically stable in the cell working conditions, for example doped tin oxides, titanium nitride and metal powders or metal coated carbons, may be added to supplement the carbons.
  • the various carbons (such as the carbon black) can also be optionally catalyzed, for example, with platinum, or alternatively a special thin layer (few micrometers) of catalyzed carbon may be printed adjacent to the titania or zirconia layers, situated underneath a conducting carbon layer that is substantially free of precious metal catalyst.
  • the catalyzed carbon paste will advantageously be made up containing a fine zirconia powder (typically having an average particle size of about 0.5 micrometers), which enhances the adhesion of the catalytic layer.
  • a fine zirconia powder typically having an average particle size of about 0.5 micrometers
  • non-conducting bulking materials such as glass spheres (e.g., having a diameter of 40-80 micrometers) may be included in the paste in order to facilitate printing of thick adhesive carbon layers of thickness 100 micrometers and above.
  • Porous carbon layer 100 includes at least three different types of carbon-based materials: graphite powder particles such as graphite particle 1, carbon black particles such as carbon black particle 2, and large leaf-like platelets of expanded graphite such as expanded graphite particle 3.
  • the various carbons may optionally be catalyzed.
  • Porous carbon layer 100 further includes titania particles, such as titania particle 4 which has been freshly generated in-situ. Without wishing to be bound by theory, we believe that such freshly generated titania strongly bonds the different materials together and to the substrate below, in those embodiments in which carbon layer 100 is sintered thereto (such as electrically insulating layer 220, shown in Figure 2).
  • Figure 3 shows that there is good electrical continuity of the carbon particles through the sintered paste, conferring a high conductivity.
  • the expanded graphite particles provide a conduit for removing the cathodic current at minimal ohmic loss.
  • titania particles may bond directly to the graphite particles, others may bond directly to the carbon black particles.
  • titania particles such as titania particles 4a may bond directly to the expanded graphite platelets such as expanded graphite particle 3, or to carbon black particles 2 or to graphite powder particles 1.
  • bonds are chemical bonds, which provide for a more robust, mechanically solid carbon layer.
  • the conductive paste includes zirconia particles and/or a zirconia precursor.
  • Figure 3 further provides a schematic representation of zirconia particles 5 disposed within sintered porous carbon layer 100.
  • the zirconia particles may be sintered to particles 1,2,3,4, providing for a more robust, mechanically solid carbon layer.
  • an exemplary, schematic cross-sectional cut away illustration of a prior art sintered porous carbon layer 105 is provided in Figure 4.
  • spheroidal graphite particles 1 and carbon black particles 2 do not provide an adequate electrically conductive network
  • titania particles 14, which were not generated in-situ are somewhat isolated and do not confer much mechanical strength to the layer 105, nor can they provide effective bonding to the substrate below, in those embodiments in which carbon layer 105 is sintered thereto (such as electrically insulating layer 220, shown in Figure 2).
  • the pastes used to produce the prior art sintered porous carbon layers may be generally difficult to screenprint, may be mechanically weak, and may not have adequate conductivity for dye cells, and more particularly, for broad, large-area dye cells.
  • the graphite powder used to produce sintered carbon layer 100 may typically include spheroidal particles having an average particle size of at least 2 micrometers, and more typically, at least 5 micrometers, up to a maximum average particle size of 10 to 15 micrometers.
  • the surface area of the graphite particles is typically 15-40 m 2 /g, and more typically, 20-30 m 2 /g.
  • the expanded graphite particles used to produce sintered carbon layer 100 may be typically anisotropic flakes having a long dimension of at least 15 micrometers, more typically at least 40 micrometers, and yet more typically at least 60 micrometers, on average.
  • the surface area of the expanded graphite particles is typically 5-50 m /g, and more typically, 25-35 m7g.
  • the carbon black particles used to produce sintered carbon layer 100 may be typically disposed in chainlike clusters of carbon, in which the individual particles may have an average primary particle size of 5-100 nm, and more typically, 10-75 nm.
  • the surface area of the carbon black particles is typically 50-2000 m 2 /g, more typically, 100-
  • the titania particles in sintered carbon layer 100 may be particles having an average primary particle size of at least 10 nm, and more typically, at least 20nm to about 30nm.
  • the surface area of the titania particles is typically 20-130 m /g, and more typically, 50-90 m 2 /g.
  • the zirconia particles in sintered carbon layer 100 may be spheroidal particles, the zirconia particles having an average particle size of at least 0.3 micrometers, and more typically, at least 0.5 micrometers, up to an upper bound of typically one micrometer.
  • the surface area of the zirconia particles is typically 5-40 m 2 /g, and more typically, 10-20 m /g. When formed in-situ, the zirconia particles are typically much smaller.
  • the weight ratio of spheroidal graphite to the sum of carbon black and expanded graphite may be preferably in the range of 1.5: 1 to 3.5: 1.
  • the weight ratio of carbon black particles to expanded graphite particles may be preferably in the range of 1.5: 1 to 1 : 1.5.
  • the weight ratio of the total carbon content of sintered carbon layer 100 (including the graphite powder, carbon black particles, and expanded graphite particles) to titanium dioxide particles may be preferably in the range of 1.2: 1 to 3.5:1.
  • the weight ratio of carbon black particles to expanded graphite particles to zirconia particles may be preferably in the range of 1.5: 1 :0.5 to 1 : 1.5: 1.
  • the weight ratio of the total carbon content and zirconia content of sintered carbon layer 100 to the titania content may be preferably in the range of 1.5: 1 to 4: 1.
  • the weight ratio of the typically spheroidal graphite particles to a sum of the carbon black particles, expanded graphite particles, and zirconia particles may be preferably in the range of 1.2: 1 to 3: 1.
  • precursor with respect to titania or zirconia, refers to a titanium-containing or zirconium-containing compound that, upon heating above at least 300C, reacts to produce titania or zirconia.
  • the term "specific surface area”, and the like, refers to the specific surface area measured by a standard BET analysis using a nitrogen medium.
  • Example 1 Preparation of a dye ceil carbon cathode according to the prior art
  • Conductive carbon black (Cabot type Vulcan XC72R, 5 gm), spherical graphite powder (Timcal, type KS4, 20 gm), and titania nanocrystalline powder (Degussa type P 90, particle size 14 nm, 4 gm) were dry blended in an agate ball mill for 30 minutes. A quantity of water (80 gm) was then added to the ball mill containing the carbon, graphite and the titania powder and milling was continued overnight. The resulting carbon paste (as a cathode paste) was evaluated for fabrication of small area dye cells (typically below 1-5 sq. cm).
  • the paste could be doctor-bladed and sintered onto conductive glass, or onto conductive glass with a lower sintered layer of porous titania covered by an upper sintered layer of porous zirconia.
  • the carbon layer was adherent for these small cells, with a conductivity of 10 ohms per square for a thickness of 50 micrometers.
  • a good efficiency of 8% under one sun illumination 100 mW per sq. cm was achieved.
  • screenprinting was attempted with the paste for larger area cells typically above 10 sq. cm. with a view to industrial scale up, the paste tended to clog the printing screens, and the print following sintering had inadequate mechanical strength and conductivity. Particularly problematic was poor adhesion to the substrate, delamination and formation of cracks and holes over the surface.
  • Spherical graphite powder (Timcal, type KS4, 20gm), carbon furnace black (Cabot, type Vulcan XC72R, 5gm) and expanded graphite (Timcal, type BNB90, 2.5 gm) were dry blended in an agate ball mill for 30 minutes.
  • a titania precursor (Dupont, TyzorTM type AA-75, 30gm) was stirred with terpineol (Aldrich, 50 gm) that contained 10wt% dissolved ethyl cellulose (Dow, ethocell type standard industrial 45). This liquid mixture was then added to the ball mill containing the carbon, spherical graphite powder, and expanded graphite, and milling was continued overnight.
  • the resulting carbon paste was screenprinted in a single printing using a plastic mesh onto a sintered porous zirconia spacer upper layer, itself part of a conducting glass carrying a sintered-on layer of nanocrystalline titania (15 micrometers thick) covered by the porous sintered zirconia layer and appropriate for dye cell fabrication for cell areas in excess of 10 sq. cm.
  • the wet thickness of the carbon print was 100 micrometers.
  • the carbon print was dried at 150C for 10 minutes.
  • the print was then sintered in air at 450C for 30 minutes, giving a sintered thickness of 50 micrometers.
  • a second printing of carbon paste, drying and sintering was carried out, and the final sintered carbon thickness was 50 micrometers.
  • Adherence of the carbon layer to the underlying zirconia layer was excellent, there was good integrity of the layer with no flaking off, and there were no cracks or holes.
  • the electrical conductivity of the layer was 10 ohms per square at this thickness. Since the conducting glass used to support the titania layer had a similar conductivity of 10 ohms per square there was good matching of photoanode and counter electrode conductivities, one of the requisites for high dye cell efficiencies.
  • the carbon layer was quite porous and allowed fast transfer of dye and electrolyte printings to the Jitania layer below. The dye cell, after dye staining of the titania, electrolyte addition and sealing, gave 7% efficiency under one sun illumination of 10OmW per sq. cm.
  • Example 3 Preparation of a screenprintable carbon dye cell cathode Spherical graphite powder (Timcal, type KS4, 20gm), carbon furnace black
  • the resulting carbon paste was screenprinted in a single printing using a plastic mesh onto a sintered porous zirconia spacer upper layer, itself part of a conducting glass carrying a sintered-on layer of nanocrystalline titania (15 micrometers thick) covered by the porous sintered zirconia layer and appropriate for dye cell fabrication for cell areas in excess of 10 sq. cm.
  • the wet thickness of the carbon print was 100 micrometers.
  • the carbon print was dried at 150C for 10 minutes.
  • the print was then sintered in air at 450C for 30 minutes, giving a sintered thickness of 50 micrometers.
  • a second printing of carbon paste, drying and sintering was carried out, and the final sintered carbon thickness was 50 micrometers.
  • Adherence of the carbon layer to the underlying zirconia layer was excellent, there was good integrity of the layer with no flaking off, and there were no cracks or holes.
  • the electrical conductivity of the layer was 10 ohms per square at this thickness. Since the conducting glass used to support the titania layer had a similar conductivity of 10 ohms per square there was good matching of photoanode and counter electrode conductivities, one of the requisites for high dye cell efficiencies.
  • the carbon layer was quite porous and allowed fast transfer of dye and electrolyte printings to the titania layer below. The dye cell, after dye staining of the titania, electrolyte addition and sealing, gave 7% efficiency under one sun illumination of 10OmW per sq. cm.
  • Spherical graphite powder (Timcal, type KS4, 21gm), carbon furnace black (Cabot, type Vulcan XC72R, 4gm) and expanded graphite (Timcal, type BNB90, 3 gm) were dry blended in an agate ball mill for 30 minutes.
  • a titania precursor (Dupont, TyzorTM type AA-75, 30gm) was stirred with terpineol (Aldrich, 50 gm) containing 10 wt% dissolved ethyl cellulose (Dow, ethocell, type standard industrial 45). This liquid mixture was then added to the ball mill containing the carbon, spherical graphite powder, and expanded graphite, and milling was continued overnight.
  • the resulting carbon paste was screenprinted using a plastic mesh onto a sintered porous zirconia spacer upper layer, itself part of a conducting glass carrying a sintered-on layer of nanocrystalline titania (15 micrometers thick) covered by the porous sintered zirconia layer and appropriate for dye cell fabrication for cell areas in excess of 10 sq. cm.
  • the wet thickness of the carbon print was 100 micrometers.
  • the carbon print was dried at 150C for 10 minutes.
  • the print was then sintered in air at 450C for 30 minutes, giving a sintered thickness of 50 micrometers.
  • Adherence of the carbon layer to the underlying zirconia layer was excellent, there was good integrity of the layer with no flaking off, and there were no cracks or holes.
  • the electrical conductivity of the layer was 10 ohms per sq. at this thickness, similar to that of the conductive glass supporting the titania layer and adequate for good dye cell performance.
  • the carbon layer was quite porous and allowed fast transfer of dye and electrolyte printings to the titania layer below.
  • the dye cell after dye staining of the titania, electrolyte addition and sealing, gave 7% efficiency under one sun illumination of 100m W per sq. cm.
  • Spherical graphite powder (Timcal, type KS4, 17gm), carbon furnace black (Cabot, type Vulcan XC72R, 4gm), carbon furnace black catalyzed with platinum (Cabot, type Vulcan XC72R containing 1% platinum, 4gm), and expanded graphite (Timcal, type BNB90, 3 gm) were dry blended in an agate ball mill for 30 minutes.
  • a titania precursor (Dupont, TyzorTM type AA-75, 80gm) was stirred with terpineol (Aldrich, 50 gm) that contained 10 wt% dissolved ethyl cellulose (Dow, ethocell, type standard industrial 45).
  • This liquid mixture was then added to the ball mill containing the carbon materials, spherical graphite powder, and expanded graphite, and milling was continued overnight.
  • the resulting carbon paste was screenprinted using a plastic mesh onto a sintered porous zirconia spacer upper layer, itself part of a conducting glass carrying a sintered-on layer of nanocrystalline titania (15 micrometers thick) covered by the porous sintered zirconia layer and appropriate for dye cell fabrication for cell areas in excess of 10 sq. cm.
  • the wet thickness of the carbon print was 100 micrometers.
  • the carbon print was dried at 150C for 10 minutes.
  • the print was then sintered in air at 450 C for 30 minutes giving a sintered thickness of 50 micrometers.
  • Adherence of the carbon layer to the underlying zirconia layer was excellent, there was good integrity of the layer with no flaking off, and there were no cracks or holes.
  • the electrical conductivity of the layer was 10 ohms per square at this thickness, similar to that of the conductive glass supporting the titania layer and adequate for good dye cell performance.
  • the carbon layer was quite porous and allowed fast transfer of dye and electrolyte printings to the titania layer below.
  • the dye cell after dye staining of the titania, electrolyte addition and sealing, gave 8% efficiency under one sun illumination of 100m W per sq. cm.

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Abstract

L'invention porte sur une pile photovoltaïque comprenant : (a) un boîtier apte à renfermer la pile photovoltaïque, comprenant une paroi de pile transparente ; (b) un électrolyte contenant une espèce redox à base d'iode, disposé à l'intérieur de la paroi de pile ; (c) au moins un revêtement conducteur partiellement transparent disposé sur une surface intérieure de la paroi de pile ; (d)une anode disposée sur le revêtement conducteur, comprenant : (i) un film poreux apte à établir un contact intime avec l'espèce redox, le film poreux comprenant des nanoparticules de dioxyde de titane chimiquement liées, et (ii) un colorant, absorbé sur une surface du film poreux, le colorant et le film étant aptes à convertir les photons en électrons ; (e) une cathode, disposée à l'intérieur d'une surface intérieure du boîtier, sensiblement opposée à l'anode, comprenant (i) une couche de carbone conductrice, et (ii) un composant catalytique, associé à la couche de carbone et apte à catalyser une réaction redox de l'espèce redox, et à transférer des électrons du composant catalytique à un composant de collecte de courant de la cathode ; la couche de carbone conductrice et une composante catalytique étant disposées en communication électrolytique, par l'intermédiaire de l'électrolyte, avec le film poreux, la couche de carbone conductrice comprenant (A) des particules de noir de charbon ; (B) de fines particules de graphite typiquement sphéroïdes ; (C) des particules de graphite expansé, et (D) des particules de dioxyde de titane, les particules de noir de charbon, les particules de graphite, les particules de graphite expansé et les particules de dioxyde de titane étant intimement mélangées, les particules de dioxyde de titane de la couche de carbone conductrice étant chimiquement liées aux particules de graphite expansé.
PCT/IL2008/000856 2007-05-15 2008-06-24 Pile sèche ayant une couche de cathode frittée WO2009001343A2 (fr)

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PCT/IL2008/000933 WO2009007957A2 (fr) 2007-07-09 2008-07-08 Pâte d'oxyde de titane sérigraphiable et traitement d'un précurseur d'oxyde de titane pour des photoanodes de cellules à colorant
PCT/IL2008/001168 WO2009027977A2 (fr) 2007-08-28 2008-08-28 Cellule photovoltaique a colorant dotee d'une contre-electrode amelioree
CN201210365063.8A CN102969167B (zh) 2007-08-28 2008-08-28 具有改善的辅助电极的光伏染料电池
CN200880113787.5A CN101842905B (zh) 2007-08-28 2008-08-28 具有改善的辅助电极的光伏染料电池
AU2009250946A AU2009250946B2 (en) 2007-05-15 2009-12-15 Photovoltaic cell

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PCT/IL2008/000671 WO2008139479A2 (fr) 2007-05-15 2008-05-15 Pile photovoltaïque

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US9257601B2 (en) 2011-05-17 2016-02-09 Mcmaster University Light emitting diodes and substrates

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US9607772B2 (en) * 2009-04-30 2017-03-28 Sharp Kabushiki Kaisha Porous electrode, dye-sensitized solar cell, and dye-sensitized solar cell module
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US9257601B2 (en) 2011-05-17 2016-02-09 Mcmaster University Light emitting diodes and substrates

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