CN102969167A - Photovoltaic dye cell having an improved counter-electrode - Google Patents
Photovoltaic dye cell having an improved counter-electrode Download PDFInfo
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- CN102969167A CN102969167A CN2012103650638A CN201210365063A CN102969167A CN 102969167 A CN102969167 A CN 102969167A CN 2012103650638 A CN2012103650638 A CN 2012103650638A CN 201210365063 A CN201210365063 A CN 201210365063A CN 102969167 A CN102969167 A CN 102969167A
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
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- 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
Abstract
A photovoltaic dye cell for converting a light source into electricity, including: (a) a housing including an at least partially transparent cell wall; (b) an electrolyte, disposed within the cell wall, containing an iodine based redox species; (c) an at least partially transparent conductive coating disposed on an interior surface of the cell wall; (d) an anode disposed on the conductive coating, and including: (i) a porous titania film adapted to make intimate contact with the redox species, and (ii) a dye, absorbed on a surface of the titania film, the dye and film adapted to convert photons to electrons; (e) a cathode disposed substantially opposite the anode, and including at least one flexible conductive carbon sheet adapted to transfer electrons to a current collection component associated with the cathode, the conductive carbon sheet disposed in electrolytic communication, via the electrolyte, with the porous titania film, wherein the conductive carbon sheet forms a discrete layer with respect to the titania film of the anode, and conforms to a contour of the film.
Description
The application is that application number is 200880113787.5, and denomination of invention is " the photovoltaic dye cell with auxiliary electrode of improvement ", the dividing an application of the Chinese patent application of application artificial " 3GSolar Photovoltaics Ltd. ".
Technical field
The present invention relates to produce from sunlight the photovoltaic dye cell of electric energy, be also referred to as DSSC.
Background technology
The dye-sensitized photovoltaic battery that produces electric energy from sunlight is disclosed for the 5th, 350, No. 644 by the people's such as Graetzel United States Patent (USP).United States Patent (USP) the 5th, 350 has instructed for No. 644 to have the photovoltaic cell that is deposited on the light transmissive conductive layer of (having used a series of titanium dioxide layer) on glass plate or the transparent polymer sheet.
United States Patent (USP) the 5th, 350, after No. 644, the United States Patent (USP) of Kay has been instructed the cell device of many series connection of arranging with that separate, parallel, narrow elongated band for the 6th, 069, No. 313 on the normal transparent substrate.Each element comprises the anode towards light that is comprised of nano-crystalline titanium dioxide, use the carbon auxiliary electrode (negative electrode) of the catalysis conductive carbon based structure of the porous that the titanium dioxide binding agent is bonded together, and place middle electric insulation porous layer based on aluminium oxide, silicon dioxide, titanium dioxide or Zirconium oxide powder with separation anode and negative electrode.After with photosensitive dye-coating nano-crystalline titanium dioxide, at least part of liquid phase, the ion migration electrolyte of being filled with of the hole in intermediate layer.Based on the current collection layer of the transparent conductive material of tin oxide between transparent substrates and anode.When anode was subject to irradiation, anode and the negative electrode of given battery provided direct voltage, so that can easily make up the series component of battery.The gap in the separately intermediate layer by separating these two elements makes the negative electrode of each continuous element be connected with the intermediate conductive layer of the anode component of front.Then use organic polymer sealed cell group, guarantee that especially the cell sealing that each independent charged pool is adjacent separates, this assembly is called as cell integrated assembly.
Usually, the dye cell above in the referenced patent than conventional photovoltaic cell conceptive more near battery cell, because the electric charge maker is separated directly contact by electrolyte.These battery pack have two electrodes that separated by electrolyte, and one of them electrode (optoelectronic pole or photo cathode) is towards the sun or light source.Each electrode supporting is on the current collector of the normally electro-conductive glass sheet of himself, and this electro-conductive glass applies thin (～0.5 micron) at face, generally based on the glass of the hyaline layer of conductive tin oxide.The electro-conductive glass sheet is as the transparent wall of dye cell.
Can replace glass to support tin oxide with transparent polymer.Optoelectronic pole or photo cathode comprise the transparent porous layer based on about 10 micron thickness (contacting with stannic oxide layer) of titanium dioxide, described titanium dioxide has the nanocrystalline feature granularity of 10-50nm, be applied on electro-conductive glass or the transparent polymer by curing, and flood specific dyestuff.Use the titanium dioxide layer that cures by a kind of form with dispersion in the following the whole bag of tricks: scraping blade method, roll extrusion, spraying, application, electrophoresis, intaglio printing, slot coated, silk screen printing or printing.The baking step that produces the highest battery performance on 450C at least, requires to support titanium dioxide layer with electro-conductive glass rather than plastics usually.Other processing procedures of titanium dioxide layer are feasible, for example reduce curing or suppressing of temperature, usually some sacrifice on efficient.What need to emphatically point out is that titanium dioxide mainly contacts with tin oxide.Exist other conductors (such as many metals, carbon and analog, even be chemically inert to electrolyte) can increase widely the charge carrier restructuring in the battery and cause serious loss in efficiency at photo cathode.Considerably less material (wherein for example tin oxide and titanium) can be used for photo cathode, because they show chemical inertness to electrolyte, and there is no defective recombinant.
To the battery of partially transparent, on its tin oxide sheet that is coated with electro-conductive glass or transparent plastic separately, relative electrode (" auxiliary electrode ") comprises catalyst (common every square centimeter of platinum that contains several micrograms) thin layer.If do not require the transparency of battery, auxiliary electrode can be opaque.For example, auxiliary electrode can be based on Trace Amounts of Platinum or another kind of catalyst advantageously carbon or the graphite of catalysis.Electrolyte in the battery normally contains the organic solvent of the redox materials of dissolving.Electrolyte typically is acetonitrile or volatile nitrile more HMW, that reduce, and redox materials is the iodine of dissolving and KI-be potassium triiodide basically in typical battery.Yet, can use other solvents, salt with mutually, the ionic liquid of essentially no vapour pressure for example, not even with redox materials.
The people's such as Graetzel United States Patent (USP) discloses multiple dye cell chemistry for the 5th, 350, No. 644, especially based on the dyestuff of ruthenium complex.Drop on this dyestuff of photon excitation on the optoelectronic pole (generating the oxidative dyestuff molecule of activation), cause that electronics enters in the conduction band of titanium dioxide and flow to (via the loaded external circuit of tool) auxiliary electrode.There, electronics is reduced into iodine with the teriodide in the electrolyte, and at the photo cathode place, teriodide is got back in the dyestuff oxidation that this iodine is activated, and stays the dye molecule for the non-activity of next photon.United States Patent (USP) the 5th, 350 discloses such dye cell No. 644 and can reach 10% electricity conversion, and obtains to surpass 11% efficient in small-sized outstanding research battery.
The battery that No. the 5th, 350,644, the people's such as Graetzel United States Patent (USP) is based on two electro-conductive glass that seal with organic bond in edge (outside the outstanding adhesive of electro-conductive glass on each face, allowing current draw).Under peak value shined upon, these batteries were with the current density operation of voltage and the 15mA/sq.cm of about 700mV, and auxiliary electrode is anodal.Material and preparation method are cheaply and the preparation of titanium dioxide layer large tracts of land but this patent is thought, so such battery may provide the good approach of low-cost photovoltaic battery potentially.The further opinion of this patent might than traditional monocrystalline or polycrystal silicon cell and even nearer film photovoltaic cell have significant cost savings, because these all are expensive and the raw material that depends on costliness and often cause environmental problem, and semi-conductor industry process equipment and the production technology of complex and expensive.These shortcomings comprise uses vacuum moulding machine and semiconductor doping method, clean room's scheme, uses poisonous hydride such as silane, hydrogen phosphide etc. as raw material, and use comprises the poisonous active layer material of cadmium, selenium or tellurium.
Ohmic loss via the electro-conductive glass that applies with tin oxide is the subject matter of dye cell.Doped tin oxide coatings as thin as a wafer, thickness is limited in below 1 micron usually, because must keep high light transmission by to photo cathode dyestuff/titanium dioxide layer.And tin oxide only is semiconductive, has about 5x10
-4The resistivity of ohm cm in addition, is difficult to adhesiveness ground bonding.Therefore, in such battery design, very undersized battery or charged pool with long and narrow active titanic dioxide band greatly Limited Current extract.
Should be pointed out that the active zone battery has some technology inferior position.For example, in the battery of above-mentioned Kay, because ohmic loss restriction, titanium dioxide band and corresponding carbon ribbon are adversely narrow (typically only have 6-8mm wide).This has caused the battery configuration of current limit and the excessive loss of the active area between battery, and the latter's loss seals the developed width of the inert material that needs owing to intercell.Under any circumstance, sufficiently sealing is still stern challenge in order to effectively prevent any intercell electrolyte between adjacent battery.
Made efforts by set level active area and the width that capable conduction is brought increases battery on the conductive glass surface upper berth, realized thus large tracts of land, wide battery configuration.The United States Patent (USP) of Kurth discloses a kind of photovoltaic cell that is arranged on conductive strips that separate, on the glass support pane that has for the 6th, 462, No. 266.With the conductive strips of slurry form printing based on silver or silver alloy, copper or copper alloy, burn till at elevated temperatures subsequently.Think that the insulating coating that forms by the glass by heavy metal free prevents that these conductive strips are subjected to the erosion of cell electrolyte.
United States Patent (USP) the 5th with respect to people such as Graetzel, 350, No. 644 disclosed batteries, United States Patent (USP) the 6th, 462, the photovoltaic cell of No. 266 instructions has the ohmic loss of reduction, because conductor belt is good conductor (such as silver slurry silk screen printing and burn till under 600 ℃), and because has increased the overall effective thickness of electric conducting material.Yet silver and the required high treatment temperature of glaze compositions have adversely affected the conductance of doped tin oxide coatings and the long-term strength characteristic of glass.Manageable glaze material is available at a lower temperature, but contains poisonous heavy metal such as lead, and also may be subjected to electrolytical erosion maybe may pollute electrolyte.In addition, be inappropriate in time by glassy layer protection silver conductor, because can not get rid of aperture fully in the glaze, especially in large-scale production process.In fact, the silver of exposure is corroded fast by the iodine in the cell electrolyte, and this adversely reduces the iodine total amount in the battery and irreversibly corrodes dyestuff, occurs similarly deteriorated in by the silver-colored line of polymer protection.
The U.S. Patent Application Publication of Goldstein has been described large tracts of land, wide electro-conductive glass or the conductive plastics that is used for dye cell for No. 20050072458.This electro-conductive glass or conductive plastics carry one group and are selected from the conductor that prevents from essence corroding the material of recombinating with charge carrier in the presence of cell electrolyte, and at this good glass or the upper deposition of titanium oxide of plastics (having the electric current collection performance of enhancing than common electro-conductive glass or plastics).By example, at first with electro-conductive glass face fluting, form the shallow grooves of one group of parallel interval.In each groove, place as the metal wire of titanium, molybdenum, tungsten, chromium or their alloy (under the battery operation condition to corrosion and charge carrier recombinate basically inertia), and use is obtaining conductance based on the thermosetting adhesive slurry that inactive ceramic adhesive (such as aluminium oxide) mixes with inertia conductive filler (such as titanium nitride) on each face of groove online and between stannic oxide layer.The slurry filling groove also overlaps on each face of groove, after solidifying like this, forms good electrically contacting with stannic oxide layer.Line is given prominence to also from the notch end of the glass edge of battery can be soldered to the electric current collection band.
In single execution mode, describe one group and be electroplated onto electro-conductive glass or the lip-deep parallel metal of conductive plastics or metal alloy band.Plating alloy prevents corrosion under the corrosive operating condition of the extreme of battery.An example of the plated metal that provides is chromium.The electric current that extracts from positive plate is generated by the side of battery again, wherein electroplates the edge seal that band passes battery hermetically.
In the further execution mode of open application, parallel conductor is band or the line of titanium, molybdenum, tungsten, chromium or their alloy of inertia.These firmly conductor dbus cross the conductive surface that uses inertia, conductivity ceramics adhesive directly to be bonded to glass.
U.S. Patent Application Publication has been expanded the line in the electro-conductive glass of the trough of belt that also is used for the battery auxiliary electrode for No. 20050072458 or has been electroplated onto the use of the band on the electro-conductive glass.Be provided with the conductive glass plate of the line that is bonded in the groove or the plating band on the conductive surface as the substrate (base) of the wide negative electrode in the dye cell, and use the electroactive Catalytic Layer of iodine is covered the plate that conductance increases.Each limit at least wide dye cell of 10-15cm becomes possibility.Yet although such negative electrode is equipped with for the suitable electric installation that extracts electric current from large-area wide battery, forcing needs the second conductive glass layer in battery, and this follows the unfavorable result of relevant cost, weight and thickness.
The existence of the current-carrying electrode of two physical separation may cause extra problem in battery.Have between the electrode of area battery of electrode at interval like this and be difficult to guarantee closely and the spacing of homogeneous (reaching homogeneous CURRENT DISTRIBUTION thus).Equally, because Full daylight is to the thermal cycle between evening (or severe cold) condition, spacing and stress may change by abnormal between the electrode of cell sealing, and is especially true for the cell electrolyte with remarkable vapour pressure.
Up to the present, the photovoltaic dye cell does not have real commercialization, although it has huge Technological Economy potential.Remaining subject matter comprises the scale of width much larger than one centimetre, area much larger than 50 square centimeters battery.And, because from the excessive ohmic loss of the tin oxide of the poor conductivity on glass or the plastics, the long-time stability of the money base conductor in the battery reach sealed cell to resist the difficulty of long-term drying and performance degradation.Many methods depend on the internal coat of the expensive transparent substrates of using conductive tin oxide, rather than use commercially available block electro-conductive glass, for example fluorine doping zinc-oxide (FTO) glass.
The further problem of dye cell in the prior art and module is the excessive surface area of waste on sealing, protective layer and the conductive path on the sunny slope of battery or module.In these cases, reactive electro miscarriage give birth to the zone usually be less than battery or module geometric area (area occupied (footprint)) 70%, caused and can utilize effective efficiency poor in the area.
Another problem of battery of the prior art be relative large interval between (especially when auxiliary electrode is with anode separates individual component) anode and negative electrode-in some cases to the wide battery of industrial applicability reach 100 microns-this has caused from electrolytical excessive ohmic loss.Should be learnt obviously that by aforementioned content when auxiliary electrode was the individual component that separates with anode in battery, auxiliary electrode required to use the second glass support usually in battery, or more adversely, used the second electro-conductive glass in battery.These have increased cost, weight and the thickness of battery widely.
Summary of the invention
According to instruction of the present invention, provide a kind of and with the ohmic loss that reduces light source has been changed into electric photovoltaic dye cell, described battery comprises: (a) chamber, described chamber is applicable to surround described photovoltaic cell, and described chamber comprises at least part of transparent cell wall; (b) electrolyte, described electrolyte are placed in the described cell wall, and described electrolyte contains the iodo redox materials; (c) at least part of transparent conductive coating, described conductive coating is arranged on the inner surface of wall; (d) anode, described anode are arranged on the described conductive coating, and described anode comprises: (i) poriferous titanium dioxide film, and it is applicable to and described redox materials close contact; (ii) dyestuff, it is absorbed on the surface of described poriferous titanium dioxide film, and described dyestuff and described film are applicable to photon is changed into electronics; (e) negative electrode, described negative electrode and described anode are oppositely arranged basically, described negative electrode comprises the conductive carbon layer that is applicable to transfer an electron to the electric current collection parts relevant with described negative electrode, described conductive carbon layer is configured to communicate with the electrolysis of described poriferous titanium dioxide film via described electrolyte, described negative electrode has the surface that arranges in the mode with respect to the surperficial direct neighbor of titanium dioxide film, and the average distance between the described surface of the surface of wherein said negative electrode and described poriferous titanium dioxide film is less than 7 microns.
According to another aspect of the present invention, a kind of photovoltaic dye cell that light source is changed into electricity with the ohmic loss that reduces is provided, described battery comprises: (a) chamber, and described chamber is applicable to surround described photovoltaic cell, and described chamber comprises at least part of transparent cell wall with inner surface; (b) electrolyte, described electrolyte are placed in the described cell wall, and described electrolyte contains the iodo redox materials; (c) at least part of transparent conductive coating, described conductive coating are arranged in described photovoltaic cell on the described inner surface of described cell wall; (d) anode, described anode are arranged on the described conductive coating, and described anode comprises: (i) poriferous titanium dioxide film, and it is applicable to and described redox materials close contact; (ii) dyestuff, it is absorbed on the surface of described poriferous titanium dioxide film, and described dyestuff and described film are applicable to photon is changed into electronics; (e) negative electrode, described negative electrode and described anode are oppositely arranged basically, described negative electrode comprises that at least one is applicable to transfer an electron to the conduction carbon plate of the flexibility of the electric current collection parts relevant with described negative electrode, described conduction carbon plate is configured to communicate with the electrolysis of described poriferous titanium dioxide film via described electrolyte, described conduction carbon plate forms discrete layer with respect to the described poriferous titanium dioxide film of described anode, and the conduction carbon plate of wherein said flexibility meets the profile of described poriferous titanium dioxide film.
According to a further aspect of the invention, a kind of photovoltaic dye cell that light source is changed into electricity with the ohmic loss that reduces is provided, described battery comprises: (a) chamber, and described chamber is applicable to surround described photovoltaic cell, and described chamber comprises at least part of transparent cell wall; (b) electrolyte, described electrolyte are placed in the described cell wall, and described electrolyte contains the iodo redox materials; (c) at least part of transparent conductive coating, described conductive coating are arranged in described photovoltaic cell on the described inner surface of described cell wall; (d) anode, described anode are arranged on the described conductive coating, and described anode comprises: (i) poriferous titanium dioxide film, and it is applicable to and described redox materials close contact; (ii) dyestuff, it is absorbed on the surface of described poriferous titanium dioxide film, and described dyestuff and described film are applicable to photon is changed into electronics; (e) electric current collection parts, it is arranged on described indoor; (f) negative electrode, described negative electrode and described anode are oppositely arranged basically, described negative electrode comprises that at least one is applicable to transfer an electron to the conduction carbon plate (or carbon-coating) of described electric current collection parts, described conduction carbon plate is configured to communicate with the electrolysis of described poriferous titanium dioxide film via described electrolyte, and wherein said electric current collection parts comprise graphite foil or thin slice or by the electric conducting material with the ratio resistivity that is lower than 1200 μ Ω cm form another kind of chemically inert, paper tinsel or the thin slice of conduction, they and the substantially parallel setting of described conduction carbon plate, described graphite foil is used for from described negative electrode collected current.
According to the further feature in the preferred embodiment of describing, this negative electrode also comprises relevant with this conductive carbon layer and is applicable to the catalyst component of the redox reaction of this redox materials of catalysis.
According to the further feature in the preferred embodiment of describing, be higher than at least 80%, at least 85%, at least 90% or at least 95% of this battery table area and obtain this distance.
According to the further feature in the preferred embodiment of describing, the average distance between this cathode surface and poriferous titanium dioxide film surface is less than 5 microns, or even less than 3 microns.
According to the further feature in the preferred embodiment of describing, this negative electrode directly contacts with the surface of this poriferous titanium dioxide film.
According to the further feature in the preferred embodiment of describing, this photovoltaic cell also comprises: (f) at least one metal tape or the line relevant with this conductive coating electricity with this anode, this band or line have enough thickness to give prominence at least 50 microns projection on the plane that is formed on the poriferous titanium dioxide film.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer forms the sheet of at least one self-supporting.
According to the further feature in the preferred embodiment of describing, the sheet of this self-supporting is only relevant physically with the poriferous titanium dioxide film of this anode.
According to the further feature in the preferred embodiment of describing, the area occupied of the single battery of this photovoltaic cell is limited by length and the width of this single battery, and wherein length and width all surpass 5 centimetres, and in some cases, at least 8 centimetres, or even at least 10 centimetres.
According to the further feature in the preferred embodiment of describing, this at least a metal tape or line are many lines, and this projection is a plurality of projections.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer forms a plurality of self-supporting bands, and this band places between this projection.
According to the further feature in the preferred embodiment of describing, wherein this band places the surperficial substantially parallel of the surface that makes this conductive carbon layer between the projection and this poriferous titanium dioxide film.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer places the porous support substrate.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer is supported by the porous support substrate that is arranged on the flexibility between the conductive carbon layer.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer and this flexible porous support substrate meet the profile of this poriferous titanium dioxide film.
According to the further feature in the preferred embodiment of describing, the surface of this negative electrode comprises the catalyst component of the redox reaction that is applicable to this redox materials of catalysis.
According to the further feature in the preferred embodiment of describing, this flexible porous support substrate comprises fiber mat.
According to the further feature in the preferred embodiment of describing, this flexible porous support substrate comprises glass fibre.
According to the further feature in the preferred embodiment of describing, this flexible porous support substrate comprises fiberglass packing.
According to the further feature in the preferred embodiment of describing, this conductive carbon layer comprises the glass fiber tape of impregnated carbon.
According to the further feature in the preferred embodiment of describing, the glass fiber tape of this impregnated carbon directly contacts with the surface of this poriferous titanium dioxide film.
According to the further feature in the preferred embodiment of describing, the conductive coating of this partially transparent is tin oxide.
According to the further feature in the preferred embodiment of describing, this photovoltaic cell also comprises the structural element of at least a conduction relevant with conductive carbon layer, this structural element has the ratio resistivity that is lower than 1200 μ Ω cm, and these parts are applicable to and are arranged to from the negative electrode collected current.
According to the further feature in the preferred embodiment of describing, these conductive structure parts comprise graphite.
According to the further feature in the preferred embodiment of describing, these conductive structure parts comprise graphite foil.
According to the further feature in the preferred embodiment of describing, this photovoltaic cell also comprises the metallic conductive element that is connected with this graphite foil, and this metallic conductive element extends through the sidewall of this battery to affect current draw.
According to the further feature in the preferred embodiment of describing, this metallic conductive element is metal forming or wire netting.
According to the further feature in the preferred embodiment of describing, placement is less than 50%, is less than 30%, is less than 20% or even less than 10% electrolyte between this anode and this negative electrode.
According to the further feature in the preferred embodiment of describing, the conduction carbon plate of this flexibility has and is lower than 90, is lower than 80 or even be lower than 70 Shore D hardness.
According to the further feature in the preferred embodiment of describing, these electric current collection parts contain and are less than by weight 2% binding agent.Preferably, these electric current collection parts contain and are less than by weight 1% binding agent, and more preferably are less than by weight 0.5% binding agent.These electric current collection parts can essentially no binding agent.
According to the further feature in the preferred embodiment of describing, this photovoltaic cell also comprises the metallic conductive element that is connected with graphite foil, and this metallic conductive element extends through the sidewall of this battery to affect current draw.
According to the further feature in the preferred embodiment of describing, this metallic conductive element is metal forming or wire netting.
Photovoltaic dye cell of the present invention can be simple, wide, large-area, efficient, cheaply, light and firmly, and can successfully solve multiple shortcoming of the prior art.
Description of drawings
The present invention only is described by embodiment with reference to the accompanying drawings herein.Now at length specifically with reference to the accompanying drawings, emphasize be shown in special case only as embodiment, and only as the purpose of the exemplary discussion of the preferred embodiment for the present invention, and be to be considered to the principle of the invention and the concept aspect is the most useful and hold intelligible description and present in order to provide.In this regard, do not plan to show in more detail CONSTRUCTED SPECIFICATION of the present invention than basic comprehension the present invention is necessary that description taken together with the accompanying drawings is so that how actual to embody several forms of the present invention be obvious to one skilled in the art.In institute's drawings attached, the symbol of same reference is used to refer to phasing element together.
In the accompanying drawings:
Fig. 1 is according to the schematic cross section of a preferred embodiment of the present invention " open type " photovoltaic dye cell;
Fig. 2 provides the schematic cross section according to the dye cell of another preferred embodiment of the present invention;
Fig. 3 a provides the schematic cross section of the Promethean photovoltaic dye cell with double plate structure;
Fig. 3 b is the schematic plan of the battery of Fig. 3 a, has shown the setting of the anchor point of this battery;
Fig. 4 is the schematic cross section according to the photovoltaic dye cell with double plate structure of another preferred embodiment of the present invention; And
Fig. 5 provides a kind of schematic cross section that has as the photovoltaic dye cell with the groove of filling conductor of cathode current means of delivery.
Specific embodiment
Can understand better with reference to the accompanying drawings principle and the operation of auxiliary electrode of the present invention and photovoltaic dye cell with the description of following.
Before explaining at least one execution mode of the present invention, should be appreciated that the present invention CONSTRUCTED SPECIFICATION and arrangements of components that be not limited to propose in the following description or in the accompanying drawings explaination in it is used.The present invention can be other execution mode or can operate in many ways or implement.Equally, should be understood that wording used herein and term are as the purpose of describing, and not will be understood that it is restriction.
One aspect of the present invention is typically to be the auxiliary electrode of wide, the large-area single dye cell of 15cm for every limit, and comprises the Promethean photovoltaic cell structure of such auxiliary electrode.We find when this class wide, the single battery assembly attempts (giving an example such as the patent of above referenced Kay with the common carbon based compositions of auxiliary electrode of the prior art, this patent with titania powder as the binding agent carbon-coating that bonds) time, except the prospective current much larger than the cell widths of 1cm extracts the restriction, the additional problem that the quite crisp character because of carbon-coating produces has also appearred.Embedding (even partly embedding) in large-area carbon-coating, not cause the total layering such as the current collection structure of wire netting, metal forming or metal wire be very difficult.This is mainly owing to the inelastic nature of inorganic binder such as the titanium dioxide that is used for the bonding carbon-coating.Because the high sintering temperature that the anode layer in the battery and cathode layer all need 450C is so usually be not suitable for more flexible organic type binding agent in this application.High sintering temperature may be destroyed organic binder bond and may use the residual contaminants battery of organic decomposition.In addition, under the dye cell condition of work, many metals are corroded by cell electrolyte, and thereby are not suitable for being used as current collector in auxiliary electrode.In the dyestuff-battery technology of Kay instruction, owing to the narrow width of charged pool these problems do not appear.In so narrow battery:
The carbon-coating that sintering is crossed (sintered-on) can show enough mechanical stabilities, and
Carbon-coating can be carried separately electric current, and does not need the current collector of assisting.
Battery structure of the present invention can comprise graphite foil, it combines non-corrosive metal (NCM) at least part of embedding graphite foil or the current draw element (current takeoff element) of metal alloy, wherein be bonded to following negative electrode carbon-coating structural conductive, or contact with its direct conduction.This structure be acceptable firmly and allow large tracts of land, wide battery configuration, in dye cell, no longer need the second conductive glass layer or the second physically separated auxiliary electrode simultaneously.The anticorrosion current draw element that embeds in the graphite foil can be selected from various shape, comprises paper tinsel, net, band or line such as many metal or alloy of titanium, the high-quality alloy of copper, tungsten, siderochrome that titanium coats or the high-quality alloy of siderochrome molybdenum.
In the another one preferred implementation, non-corrosive metal (NCM) or metal alloy current draw element can be used as independently auxiliary electrode and need not in conjunction with carbon or graphite foil layer in battery, in this case, and with the auxiliary electrode of the direct catalysis of Trace Amounts of Platinum.
Fig. 1 has shown the schematic cross-sectional view of an execution mode of Promethean photovoltaic dye cell 100, and this battery can be a kind of " open type " sandwich-like pattern.Be 1mm-3mm in the anode-supported glass 102(of support glass such as routine typical thickness) on, being provided with thin, transparent conductive surface layer 104, this layer is based on for example tin oxide.Support glass 102 and conductive surface layer 104 can provide the conductance Enhanced feature and (for example describe in No. the 20050072458th, the above referenced U.S. Patent Application Publication, this patent is incorporated at this by reference based on whole purposes, just looks like that they are by open in full).Support glass 102 is as the substrate of this dye cell and basic part.With this substrate fluting and line current extraction element as instructing in the above referenced patent disclosure is installed.Thereby, pass battery to the side seal of line by battery, and combine and/or by for example being welded to connect to electric current collection band (not shown), in order to form the galvanic anode binding post.Use adhesive composition 112 inertia, conduction in each groove 108, said composition 112 is connected to line 116 in the groove, and so that has good bridging with stannic oxide layer electrically contact on each face of this groove.As an embodiment, titanium, tungsten or high-quality alloy wire can be inserted in the groove.Preferably include such as the conductor of titanium nitride with such as the conductive adhesive of the binding agent of aluminium oxide and also can be added in the groove.Usually by the silk screen printing of slurry, then dry and sintering applies the nano-crystalline titanium dioxide layer on the tin oxide surface.
Porous sintered nanocrystalline titanium dioxide film or layer 120 are designed to have about 15 microns typical thickness.Titanium dioxide film or layer 120 can comprise some layers of titanium dioxide subgrade, and each subgrade is silk screen printing and sintering by oneself.We found that before applying the nano-crystalline titanium dioxide layer upper surface that covers conductive adhesive 112 with insulating barrier 124 can help to eliminate the possible short circuit that occurs between anode and negative electrode.Insulating barrier 124 may be even more important to as shown in Figure 1 the wherein conductive adhesive surface battery far above sintered titanium dioxide layer 120.
Insulating barrier 124 optional glaze or adhesive compositions from containing quite coarse titanium dioxide, zirconia, aluminium oxide or the silica dioxide granule of the feature granularity that preferably has a few micron number magnitudes, or selectively, be selected from high temperature polymer such as polyimides or siloxanes.Can be used for subsequently covering titanium dioxide layer 120 from the porous insulation wall of the silk screen printing of the slurry that contains relatively coarse titanium dioxide, zirconium dioxide, silicon dioxide or alumina particle.The wall of design silk screen printing is about 5 microns sintering insulated wall 128 to generate thickness.Sintering insulated wall 128 also plays the effect of light scattering layer, and guiding light is got back to sintering nano-crystalline titanium dioxide layer 120.
Use auxiliary electrode layer by silk screen printing first and continue to construct battery.Wall 128 can be narrow, and usually in 2-10 micron number magnitude, to guarantee anode/cathode interval very little in the battery, low Ohmic resistance and high battery fill factor, curve factor, all these helps to strengthen battery performance.But on dielectric spacer layer 128, can come via the slurry of the silk screen printing that contains inert binder the porous carbon layer of application of thin, randomly by the porous carbon layer of Trace Amounts of Platinum or the catalysis of platinum catalyst substitute.Dry and this thin layer of sintering only has the sintered porous catalysis carbon-coating 132 of several microns characteristic thickness with generation.
But but be to use relatively thick porous, electrically conductive carbon-coating via the carbon pastes of the silk screen printing that contains inert binder behind the porous catalytic carbon pastes layer sintering of silk screen printing.Carry out another sintering step, this produces sintered porous conductive carbon layer 136.Typically design the silk screen printing of this carbon pastes so that the thickness of the conductive carbon layer 136 of sintering typically is about the 50-100 micron.
One preferred embodiment in, if possible can be in single sintering step, at 450 ℃ of lower each layers of sintering, behind the Local cooling, via porous carbon layer 136 the sensitizer dyestuff is introduced in the titanium dioxide layer 120.Can be with having a slice graphite foil 140 that prepare, that sintering is crossed, porous, conductive carbon (with chemically inert) adhesive layer 144 and place on the carbon-coating 136 its lower being provided with, in order to form good conductive contact with carbon-coating 136.
Being the band of line, net, band, perforation or non-corrosive metal (NCM) or the metal alloy current collector 152 of paper tinsel form can embed in the graphite foil at least in part, and these current collector 152 outstanding battery seals (hereinafter describing) of periphery that pass are with the auxiliary electrode binding post as battery.We find that in normal battery-operated situation the copper that titanium, titanium coat and tungsten and the high-quality alloy that some mainly are comprised of ferrochrome or ferrochrome molybdenum can be used as the current collection material of chemically stable auxiliary electrode.
Sheet (sheet) 154 can be arranged on the top of assembly with enclosed cell.Sheet 154 can be made by the glass pane of cheapness or various metals or alloy.Top in sheet 154 times and graphite foil 140 can be advantageously provided flexure strip 148, and flexure strip 148 preferably includes foam, fiber mat or elastomeric pad or expansion precursor material or expanded polymer material or is comprised of these materials.The flexure strip 148 that can comprise polymer, carbon or metal material is compressible and the picture spring, to help at the relative uniformly pressure of 136 maintenances of graphite foil 140 and carbon-coating, guarantees enough electrically contacting and abscission layer 136 not at large necessary area simultaneously.
The edge of battery 100 can seal by peripheral seal 156, for example uses the liquid phase sealant.Electrolyte can be introduced in the battery 100 subsequently, typically uses vacuum mode via the hole (not shown) on the sheet 154, and the sealing compositions sealing can be used in this hole.Battery can be used for test/modularity subsequently.
Fig. 2 has shown the schematic cross section according to the photovoltaic dye cell 200 of another preferred embodiment of the present invention.Support that at the anode of support glass such as routine glass 202(typical thickness is 1mm-3mm) on, being provided with thin, transparent conductive surface layer 204, this layer is based on for example tin oxide.Can provide the support glass 202 of conductance Enhanced feature as the substrate of dye cell 200 and basic part.At conductive surface layer 204 one group of substantially parallel metal or alloy band 216 that cell electrolyte and charge carrier restructuring is inertia that separate, preferred is set.Can be by plating mode deposition be with 216 to provide the electric current conveying device for battery 200.Sealably pass the side of battery 200 with 216, and can be electrically connected, for example by the outer electric current collection band (not shown) of seal, form thus the anode terminal of battery.Basically be described about filling groove shown in Figure 1 as mentioned, the band of electroplating also can advantageously be coated with insulating layer coating 228, for example comprises that the glaze of titanium dioxide, zirconia, aluminium oxide and/or silicon dioxide or adhesive composition are to prevent the short circuit of anode/anode.Usually by screen printing sizing agent, drying and sintering the nano-crystalline titanium dioxide layer is applied on the conductive surface layer 204.
The sintering nanocrystalline titanium dioxide film of porous or layer 220 are designed to have about 15 microns typical thickness.Titanium dioxide film or layer 220 can comprise some titanium dioxide subgrades, and each subgrade is silk screen printing and sintering by oneself.
Then the porous insulation wall with silk screen printing covers titanium dioxide layer 220, and this wall experience sintering is to generate sintering insulated wall 228.The slurry of this silk screen printing can contain relatively coarse titanium dioxide, zirconia, silicon dioxide and/or alumina particle.Behind drying and the sintering, sintering insulated wall 228 can have the thickness of about 2-10 micron.Design this thickness to guarantee anode/cathode interval very little in the battery.Further this thickness of design improves battery performance thus to obtain low internal resistance and high battery fill factor, curve factor.Wall 228 also plays the effect of light back scattering layer, and guiding light is got back to sintering nano-crystalline titanium dioxide layer 220.
Negative electrode or the auxiliary electrode 260 of battery 200 are set at dielectric spacer layer 228.Negative electrode 260 comprises sintered porous catalysis conductive carbon layer 232, and this carbon-coating 232 can contain composition to battery 200 and be chemically inert binding agent and can be by Trace Amounts of Platinum or the catalysis of platinum catalyst substitute.The thin layer of can be by silk screen printing or otherwise applying the porous catalytic carbon pastes prepares carbon-coating 232, this layer of subsequent drying and sintering.Sintered porous conductive carbon layer 232 can have several microns thickness, typically less than about 10 microns.At catalysis carbon-coating 232 relatively thick sintering conductive carbon layer 236 is set, this carbon-coating 236 also can form the part of negative electrode 260.Can prepare carbon-coating 236 by silk screen printing, this layer of subsequent drying and sintering is to obtain the typical thickness of 50-100 micron.
Some high surface area carbon and graphite are so active so that can get rid of layers 228 needs to the catalysis that separates or platinum plating to the redox reaction of iodine in battery.
In a preferred embodiment, typically or preferably under 450 ℃, each layer of sintering in single sintering step behind the Local cooling, introduced the sensitizer dyestuff in the titanium dioxide layer 220 via porous carbon layer 236.Then, via conductive carbon tack coat 245 with a slice graphite foil 240 conductivity be bonded to carbon-coating 236, it is curable that this tack coat 245 can be selected under 120 ℃ temperature, avoids thus the heat sensitive dye in the titanium dioxide layer 220 is caused any infringement.The suitable component of tack coat 245 can comprise carbon dust and based on inertia (with respect to the electrolyte) inorganic binder of aluminium oxide or based on inertia (with respect to the electrolyte) organic binder bond of for example siloxanes or polyimides.
Can consider the part with graphite foil 240 and conductive carbon tack coat 245 formation negative electrodes 260.
Be the band of line, net, band, perforation or non-corrosive metal (NCM) or the metal alloy current collector 252 of paper tinsel form and can embed in (at least in part) graphite foil 240, these current collector 252 outstanding battery seals (hereinafter describing) of periphery that pass are with the auxiliary electrode binding post as battery 200.We find that copper that titanium, titanium coat and tungsten and the high-quality alloy that some mainly are comprised of ferrochrome or ferrochrome molybdenum can be used as the current collection material of chemically stable auxiliary electrode.Graphite foil 240 can advantageously have perforation 246 and enter in the battery to be conducive to electrolyte distribution.Can carry out the electrolyte filling step in this stage.
By placing a slice plastics stratiform paper tinsel 258 and using periphery sealants 252 and finish battery from structure the element 202 of battery and 258, or selectively, can spray the polymeric seal layer in order to seal first this battery and provide extra sealing with external metallization paper tinsel (not shown).Yet if light weight construction is not crucial especially, glass pane or metal/alloy sheet can be used for airtight this battery so, and under latter event, can omit current collector 252.
As previously mentioned, have the anode of physically separation and large-area, the wide dye cell of auxiliary electrode and may stand various distinctive performance limitations.Reducing or eliminating this physical separation is a purpose of open type sandwich-like design as illustrated in fig. 1 and 2, and all active layers all are glued on independent (conduction) sheet glass in this design.In the commercial Application of wide battery, especially to use in the non-volatile electrolytical battery, interelectrode spacing is tended at least 50-100 micron, and at this some place, the ohmic loss of cell electrolyte becomes excessive.Similarly, the variations in temperature between evening on daytime may cause that the expansion/contraction of spacing between electrode changes, and this may cause, and electric current is irregular to be added stress with sealing place.
Yet, one preferred embodiment in, we disclose a kind of photovoltaic dye cell with the design of two plates, this photovoltaic dye cell can overcome these restrictions.
Although the multiple sandwich that is printed with carbon-coating on the zirconia wall on the titanium dioxide layer can allow the tight spacing of carbon and titanium dioxide surface, must emphasize that such structure very easily makes the carbon printed layers be penetrated into conductive glass surface via any hole or defective in titanium dioxide or the interval printed layers.The conductive surface that the carbon printed layers is penetrated into FTO glass causes this battery short circuit, reduces thus or the restriction battery performance.Consider the life-span that reaches the needed at least 7-10 of commercial viability for battery, this problem is especially serious.The Promethean double plate structure of describing has herein been eliminated this important and potential key issue, because the carbon auxiliary electrode is not sintered (for example, at high temperature chemical bonding) on titanium dioxide or interval printed layers.On the contrary, the carbon auxiliary electrode be place wall top and can the physical contact wall, or place the upper surface of titanium dioxide layer, but not different on wall or the titanium dioxide layer of chemical bonding and independently entity, as in the printing carbon-coating technology.
Such as what use in herein specification and claims subsequently part, with respect to the surface of negative electrode and the surface of anode (for example poriferous titanium dioxide film of the carbon surface of the carbon surface of negative electrode or catalysis and anode), term " direct neighbor " refers to the surface of not separated by intercalation.
Such as what use in herein specification and claims subsequently part, with respect to cathode layer and/or anode layer, term " only physically relevant " refer to contacted but be not sintered together and otherwise by chemically separated layer.
Such as what use in herein specification and claims subsequently part, with respect to the band of negative electrode or the layer of layer and/or anode, term " self-supporting " refers to band or layer and remains on appropriate location in the battery about relative electrode with isolating construction.
Such as what use in herein specification and claims subsequently part, with respect to layer adjacent in the battery, term " disperses " to refer to and can contact with each other but different layer still physically.
Fig. 3 a provides the schematic cross section of an execution mode of Promethean like this photovoltaic dye cell 300.Anode glass 302 with typical thickness of 1mm-3mm has thin, the transparent conductive surface layer 304 based on electric conducting material such as tin oxide.Anode glass 302 and conductive surface layer 304 can provide the feature that conductance strengthens.With electro-conductive glass fluting and basically foregoing line current extraction element is installed.Thereby, line the side seal of this battery pass battery, and knitted together and/or by for example being welded to connect to electric current collection band (not shown), to form the anode terminal of battery 300.In each groove 308, use conductive adhesive layer 312, this layer preferably is chemical inertness to cell electrolyte and plays wire 316 is connected to effect in the groove 308, simultaneously so that have good bridging with stannic oxide layer (conductive surface layer 304) electrically contact on each face of groove 308.As an embodiment, titanium, tungsten or high-quality alloy wire can be inserted in the groove 308, and preferably include such as the conductor of titanium nitride with such as the conductive adhesive of the binding agent of aluminium oxide and also can add in the groove 308.
In structure battery 300, before applying the nano-crystalline titanium dioxide layer, can cover with insulating barrier 324 upper surface of conductive adhesive layers 312, be short-circuited between anode and negative electrode preventing.When the surface of conductive adhesive layer 312 during far above sintering nano-crystalline titanium dioxide layer 320 (shown in Fig. 3 a), this is even more important.
Insulating barrier 324 is optional from containing glaze or the adhesive composition of quite coarse titanium dioxide, zirconia, aluminium oxide or the silica dioxide granule of the feature granularity with several microns, or selectively, is selected from high temperature polymer such as polyimides or siloxanes.Apply the nano-crystalline titanium dioxide layer on tin oxide surface (conductive surface layer 304), this is normally by screen printing sizing agent, and subsequent drying and sintering are to generate sintering nano-crystalline titanium dioxide layer 320.This sinter layer is designed to have about 15 microns typical thickness behind sintering step.Based on the purpose of electric insulation and/or light back scattering, titanium dioxide layer 320 optionally is coated with the coarse particles layer (not shown) based on titanium dioxide, zirconia, aluminium oxide or silicon dioxide.In the construction process of battery 300, available sensitizer dyestuff covers titanium dioxide layer 320 subsequently, and this step can be carried out subsequently, before filling electrolyte.With non-corrosive metal (NCM) sheet 368 closing batteries, this sheet metal has used for example conventional catalysis of catalyst of Trace Amounts of Platinum crystallite 332, and uses the sealant 336 of electrolyte-resistant to be sealed to anode glass 300 in each edge with this.Suitable constructions material as sheet metal 368 can comprise copper, the tungsten that titanium, titanium coat or mainly comprise siderochrome or the high-quality alloy of siderochrome molybdenum.
Importantly, by using the adhesive 340 of one deck electrolyte-resistant, sheet metal 368 is bonded to the electrical insulating material of the rising of insulating barrier 324.Suitable adhesive is available, for example based on siloxanes or polyimides.Can place adhesive phase 340 to keep firmly anchoring and uniform spacing at sheet 368 and 302 of anode glass with periodic intervals along the material that covers groove 308.Laterally continuous adhesive phase is exercisable, yet, but may be disadvantageous, because it is with the electrolyte between hydraulic way isolation adjacent grooves, and electrolyte filling battery 300 is quite required great effort.
Fig. 3 b has shown the setting of the anchor point in the schematic plan of battery 300, and wherein each "+" mark 303 represents to be placed with the spacing position of the groove of adhesive on positive plate.
Sheet 368 among Fig. 3 a can be slotted in anode glass 302 in the mode of complementation, in order to as accept the profile of the rising of insulating barrier 324, the close proximity (only having tens microns) that realization is expected between the surface of the surface of catalyst 332 and titanium dioxide layer 320 thus with requiring.Battery can be filled electrolyte via the hole (not shown) of sheet metal 368, subsequently closed hole.
According to the separation criteria of expectation, the various selectable execution mode that makes up two plate designs all is possible.In Fig. 3 a, positive plate can be mounted conductive metal band, rather than the line that embeds.Similarly, can be the pattern of picture groove by punch forming simply based on the sheet metal of auxiliary electrode.One preferred embodiment in, auxiliary electrode can be the flat sheet metal of mild catalytic, from the sheet metal punching or cut out slit, so that slit is installed on the ascending member that is positioned on the groove, make simultaneously catalytic surface between slit and following titanium dioxide surface reach close proximity.Under these circumstances, be placed on the glass on the plate of slit or polymer sheet and will be used for closing battery, and this glass or polymer will be anchored to a plurality of somes place on the ascending member.
Fig. 4 provides the schematic cross section of two plate photovoltaic dye cells 400 according to another implementation of the invention.The configuration of this pair plate battery can only use single electro-conductive glass sheet by each battery.This configuration is further realized the very closely juxtaposition of anode and negative electrode.It is can tool spaced to be coated with the photo cathode support glass of conductor layer 404 of substantial transparent or substrate 402, the line 410 of preferred parallel, the conductive adhesive layer of this line by inertia basically for example conductivity ceramics adhesive phase 415 is bonded in the lip-deep correct position (for example, on the top of conductor layer 404) of electro-conductive glass.The nanocrystalline porous titanium dioxide layers 406 of sintering that are generally the 10-15 micron thickness between the edge of chemically inert current collection line 410 and battery 400.Because line 410 can typically have at least 100 microns diameter, and the height of titanium dioxide layer 406 typically is lower than about 15 microns, so line 410 can be outstanding above 80 microns at titanium dioxide layer 406.For fear of the short circuit of the auxiliary electrode 430 of battery 400, can advantageously use electric insulation layer 418, for example comprise that zirconic layer covers ceramic binder layer 415.Electric insulation layer 418 can typically have the thickness in the 20-50 micrometer range.
Can affect current draw from negative electrode or auxiliary electrode 430 via the graphite foil 435 on the band that places porous cathode layer 425 (and usually with respect to band physical separation).In its periphery, graphite foil 435 can have inert metal net or paper tinsel 440 at least part of embedding, that may give prominence to outside battery 400 and collect with the promotion cathode current.
Can make dye cell 400 according to following Promethean method: have the transparent stannic oxide layer of transparent conductor layer 404(such as conduction) the surface of photo cathode support glass 402 are screen printing brushes of titania slurry.In case sintering generates the isolated band of sintered porous titanium dioxide layer 406.Current collection line 410 is arranged in each gap of adjacent titanium dioxide interband.Can be around the chemically inert conductivity ceramics slurry of line 410 printings.Can be at the top of ceramic material printing electric insulation slurry.Sintering operation makes 415 chemical bonding of ceramic binder layer to transparent conductor layer 404.Sintering makes electric insulation layer 418 chemical bondings to ceramic binder layer 415.
In this, the titanium dioxide band may be stained by dyestuff.
The auxiliary electrode of battery 400 comprise place titanium dioxide layer 406 with on the band of porous, electrically conductive layer 425.These bands can advantageously comprise and flood the fiberglass packing that experiences the conductive carbon pastes of sintering.The band of conductive layer 425 can use Catalytic Layer 432 by advantageously catalysis, and this Catalytic Layer 432 can be included in its lip-deep Trace Amounts of Platinum catalyst.These bands can directly place on the sintered titanium dioxide layer 406 of photo cathode, and wherein Catalytic Layer 432 arranges towards titanium dioxide layer 406.Although this direct contact, we find that in the band of impregnated carbon it is unnecessary that carbon and titanium dioxide are further isolated.
Via place conductive layer 425 with on graphite foil 435 advantageously finish current draw.Graphite foil 435 has inert metal net or the paper tinsel 440 of the embedding that can pass hermetically this battery in its periphery.Come sealed cell 400 by glass pane lid 445 together with internal edge seal 465 and external margin seal 470, the polymer that preferably applies by two kinds of orders produces.Glass cover 445 applies enough pressure to guarantee good the electrically contacting and spacing closely of element in the battery to following graphite foil.Electrolyte adds in the battery and can be undertaken by the filler opening (not shown) on the glass pane, and its mesopore is subsequently by polymeric seal.Extraction terminal 442 via the wall outside of battery 400 extracts cathode current from this battery, and described terminal is by forming by the wire netting of cell wall or the sealable projection of paper tinsel 440, as passing through edge seal 465 and 470.Can will can be soldered to electric current collection band (not shown) via edge seal 465 and the 470 independent lines from the salable appearance of photo cathode to form the photo cathode current collector.
In solar energy module, single battery can be electrically connected or be installed on the supporting construction aptly.
Obviously draw according to foregoing, negative electrode 430 forms discrete, physically separated layer with respect to the poriferous titanium dioxide film 406 of anode.Negative electrode 430 also is applicable to show compressibility and flexible value.To form a sharp contrast with the negative electrode of essentially no productive rate in the prior art and (wherein to damage in order preventing; negative electrode must keep certain distance with the surface of the crisp poriferous titanium dioxide film of anode); negative electrode 430(and the especially band of conductive layer 425) can be retained as the surface of leaning on poriferous titanium dioxide film 406, and can absorb for poriferous titanium dioxide film 406 normal modest pressures in order to protect titanium dioxide film 406.In addition, the bottom surface of negative electrode 430 can be fit to or meet the profile of titanium dioxide film 406, so that it is inefficient to have reduced significantly the serious ohm that characterizes various dye cells of the prior art.
In order to make band reach the necessary degree of consistency, the band of conductive layer 425 can have and is lower than 90 Shore D hardness.In some cases, the band of conductive layer 425 can have and is lower than 80, or is lower than 70 Shore D hardness.
In the schematic cross section according to the photovoltaic dye cell of another preferred embodiment of the present invention as shown in Figure 5, the same anode part that makes up with Fig. 3 a basically.Auxiliary electrical pole plate or lid comprise glass pane 578, by peripheral seal 556, in edge this glass pane are bonded to anode glass 302 as using fluid sealant.For the purpose of electric insulation and light back scattering, can use the nano-crystalline titanium dioxide layer 320 based on coarse particles layer 322 coated anode of titanium dioxide, zirconia, aluminium oxide or silicon dioxide.Before electrolyte is filled, available sensitizer dye-coating nano-crystalline titanium dioxide layer 320 subsequently, or this step can be carried out subsequently.On the cathode plane of battery 500, contain by conductive adhesive layer 592 such as each groove at least one groove of groove 588 and to be bonded in wire 596 on the correct position, wherein this adhesive phase also extends as pantostrat spread all over glass surface in order to conductance is provided in adjacent grooves.By layer of adhesive 566, anode and opposite plate can be bonded together at different point (interval such as periodic intervals) with anti-groove (counter groove) (from the same in Fig. 3 a) along anode.Between adjacent grooves, the layer 570 of carbon or graphite is provided, randomly be coated with catalyst, such as Trace Amounts of Platinum, and the thickness of selecting this layer is to allow carbon or catalyst surface and nano-crystalline titanium dioxide layer 320 close proximity.Battery 500 can be filled electrolyte by the filler opening (not shown) in the auxiliary electrode, seals subsequently this hole, and at this moment, battery 500 can be prepared for test and modularity.Exist the anchor point closely placed (as, at the area battery that is of a size of 15cm * 15cm about 1cm of being separated by) and use strong binding agent such as siloxanes in battery 500, to keep spacing and prevent short circuit.
Although described the present invention in conjunction with specific execution mode, many replacement schemes, modifications and variations are obvious to one skilled in the art.Therefore, expectation comprises all such replacement schemes, modifications and variations.All publications of mentioning in this specification and patent at this by to be incorporated in the specification in full with incorporating clearly and individually by reference herein as each independent publication or patent into identical degree is quoted.In addition, in this application any reference quotes or confirms and should not be interpreted as admitting that such reference is available as prior art of the present invention.
Claims (14)
1. the ohmic loss with reduction changes into electric photovoltaic dye cell with light source, and a single photovoltaic dye cell of described battery comprises:
(a) chamber, described chamber is applicable to surround described photovoltaic cell, and described chamber comprises at least part of transparent cell wall with inner surface;
(b) electrolyte, described electrolyte are placed in the described cell wall, and described electrolyte contains redox materials;
(c) at least part of transparent conductive coating, described conductive coating are arranged in described photovoltaic cell on the described inner surface of described at least part of transparent cell wall;
(d) anode, described anode are arranged on the described conductive coating, and described anode comprises:
(i) poriferous titanium dioxide film, it is applicable to and described redox materials close contact; And
(ii) dyestuff, it is absorbed on the surface of described poriferous titanium dioxide film, and described dyestuff and described poriferous titanium dioxide film are applicable to photon is changed into electronics;
(e) negative electrode, described negative electrode and described anode are oppositely arranged, and described negative electrode comprises that at least one is applicable to transfer an electron to the conduction carbon plate of the flexibility of the electric current collection parts relevant with described negative electrode,
(f) at least one metal tape or line, it is relevant with described conductive coating electricity with described anode,
Described conduction carbon plate is configured to communicate with the electrolysis of described poriferous titanium dioxide film via described electrolyte,
Described conduction carbon plate forms discrete physically different layer with respect to the described poriferous titanium dioxide film of described anode,
Wherein, the conduction carbon plate of described flexibility is suitable for consistent with the profile of described poriferous titanium dioxide film,
Wherein, the length of described single battery and width are all at least 5 centimetres or at least 10 centimetres.
2. photovoltaic cell as claimed in claim 1, described photovoltaic cell also comprises:
Described at least one metal tape or line have enough thickness with outstanding at least 50 microns projection on the plane that is formed on described poriferous titanium dioxide film.
3. photovoltaic cell as claimed in claim 1, described at least one metal tape or line are many lines, and described projection is a plurality of projections.
4. photovoltaic cell as claimed in claim 3, described conduction carbon plate forms a plurality of self-supporting bars, and described self-supporting bar is arranged between the described projection.
5. photovoltaic cell as claimed in claim 4, described self-supporting bar is arranged on the described flush of between the described projection so that the surface of described conduction carbon plate and described poriferous titanium dioxide film.
6. such as the described photovoltaic cell of claim 1-5, described conduction carbon plate is supported by the porous support substrate of flexibility, and the porous support substrate of described flexibility comprises fiber mat and glass fibre.
7. such as the described photovoltaic cell of claim 1-5, wherein said electric current collection parts contain and are less than by weight 2%, are less than 1%, perhaps are less than 0.5% binding agent, perhaps binder free.
8. such as the described photovoltaic cell of claim 1-5, wherein said conduction carbon plate comprises the glass fiber tape of impregnated carbon, and the glass fiber tape of wherein said impregnated carbon directly contacts with the described surface of described poriferous titanium dioxide film.
9. such as the described photovoltaic cell of claim 1-5, the surface distance of the surface of described negative electrode and described poriferous titanium dioxide film is less than 7 microns, less than 5 microns, or less than 3 microns, perhaps the surface of described negative electrode directly contacts with the surface of described poriferous titanium dioxide film.
10. such as the described photovoltaic cell of claim 1-5, the lid of wherein said single battery is suitable for the close space length of exerting pressure and being suitable for promoting element in the described photovoltaic dye cell to described electric current collection parts.
11. such as the photovoltaic cell of claim 1-5, described electric current collection parts comprise graphite foil.
12. such as the photovoltaic cell of claim 4 or 5, wherein graphite foil is discrete with respect to described self-supporting bar physics.
13. photovoltaic cell as claimed in claim 11 also comprises the metallic conductive element that is connected with described graphite foil, described metallic conductive element extends through the sidewall of described photovoltaic dye cell to affect current draw.
14. photovoltaic cell as claimed in claim 13, wherein said metallic conductive element are metal forming or wire netting.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96831607P | 2007-08-28 | 2007-08-28 | |
| US60/968,316 | 2007-08-28 | ||
| ILPCT/IL2008/000671 | 2008-05-15 | ||
| PCT/IL2008/000671 WO2008139479A2 (en) | 2007-05-15 | 2008-05-15 | Photovoltaic cell |
| ILPCT/IL2008/000856 | 2008-06-24 | ||
| PCT/IL2008/000856 WO2009001343A2 (en) | 2007-06-24 | 2008-06-24 | Dry cell having a sintered cathode layer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104485230A (en) * | 2014-12-18 | 2015-04-01 | 中国科学院上海硅酸盐研究所 | Novel counter electrode for dye-sensitized solar cell and preparation method thereof |
| CN115349156A (en) * | 2020-04-17 | 2022-11-15 | 埃塞格制造有限公司 | Photovoltaic device |
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| CN102754273B (en) * | 2010-02-03 | 2015-05-06 | 新日铁住金化学株式会社 | Dye-sensitized solar cell and method for manufacturing the same |
| US9129751B2 (en) * | 2010-03-29 | 2015-09-08 | Northern Illinois University | Highly efficient dye-sensitized solar cells using microtextured electron collecting anode and nanoporous and interdigitated hole collecting cathode and method for making same |
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| KR101132032B1 (en) * | 2010-08-11 | 2012-04-02 | 삼성에스디아이 주식회사 | Electrode for photoelectric conversion device, method of preparing the same and photoelectric conversion device comprising the same |
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| FR3082356B1 (en) * | 2018-06-11 | 2020-06-19 | Armor | PROCESS FOR MANUFACTURING A PHOTOVOLTAIC MODULE AND PHOTOVOLTAIC MODULE THUS OBTAINED |
| CN115764003B (en) * | 2022-10-11 | 2023-07-21 | 贵州梅岭电源有限公司 | Zinc-silver accumulator used for multiple times under microgravity environment |
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| US20050092359A1 (en) * | 2002-06-04 | 2005-05-05 | Nippon Oil Corporation | Photovoltaic device |
| US20050072458A1 (en) * | 2003-01-12 | 2005-04-07 | Orionsolar Ltd. | Solar cell device |
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| CN104485230A (en) * | 2014-12-18 | 2015-04-01 | 中国科学院上海硅酸盐研究所 | Novel counter electrode for dye-sensitized solar cell and preparation method thereof |
| CN115349156A (en) * | 2020-04-17 | 2022-11-15 | 埃塞格制造有限公司 | Photovoltaic device |
| CN115349156B (en) * | 2020-04-17 | 2023-08-15 | 埃塞格制造有限公司 | Photovoltaic device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101842905A (en) | 2010-09-22 |
| WO2009027977A2 (en) | 2009-03-05 |
| WO2009027977A3 (en) | 2009-04-30 |
| CN101842905B (en) | 2013-01-16 |
| WO2009027977A4 (en) | 2009-06-11 |
| CN102969167B (en) | 2016-08-03 |
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