WO1993020569A1 - Photovoltaic cells - Google Patents

Photovoltaic cells Download PDF

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Publication number
WO1993020569A1
WO1993020569A1 PCT/EP1993/000731 EP9300731W WO9320569A1 WO 1993020569 A1 WO1993020569 A1 WO 1993020569A1 EP 9300731 W EP9300731 W EP 9300731W WO 9320569 A1 WO9320569 A1 WO 9320569A1
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WIPO (PCT)
Prior art keywords
component
poly
hereinafter
polymer
photovoltaic
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Application number
PCT/EP1993/000731
Other languages
French (fr)
Inventor
Rolf Hasler
Victor Sanahuja
Original Assignee
Sandoz Ltd.
Sandoz-Patent-Gmbh
Sandoz-Erfindungen Verwaltungsgesellschaft M.B.H.
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Publication of WO1993020569A1 publication Critical patent/WO1993020569A1/en

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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
    • H01G9/2027—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
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2086—Photoelectrochemical cells in the form of a fiber
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • H10K30/53—Photovoltaic [PV] devices in the form of fibres or tubes, e.g. photovoltaic fibres
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/143—Polyacetylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to new Ti0 2 containing photovoltaic cells effective in the conversion of visible light to electric energy.
  • a photovoltaic cell comprising:
  • component a an electrically conductive element on to which one or more titanium dioxide layers have been applied (hereinafter component a);
  • component b a solid electrolyte (hereinafter component b);
  • component c an electrically conductive element through which light can pass to the Ti0 2 layer (hereinafter component c).
  • photovoltaic cell (hereinafter the photovoltaic coaxial cell) comprising
  • a cylindrical conductive element eg a textile conductive filament or a wire such as copper wire
  • component x a cylindrical conductive element on to which one or more titanium dioxide layers have been applied
  • component bj a solid electrolyte that has been applied concentrically around the cy-tad-rical component a, (hereinafter component bj);
  • component a) comprises a support, (preferably a glass plate coated with metal oxide, a metal surface or a polymer sheet (preferably an intrinsically conductive polymer)) to which the Ti0 2 layer is applied.
  • component a) is transparent.
  • transparent is meant that at least 60%, preferably 70%, more preferably at least 80%, especially 80-98% of incident light passes through the glass.
  • the Ti0 2 layer comprises rutile and anatase, more preferably anatase.
  • the titanium dioxide is doped with a metal ion, which may be selected from a divalent or trivalent metal or boron.
  • a metal ion which may be selected from a divalent or trivalent metal or boron.
  • Preferred dopant is aluminium.
  • the titanium dioxide layers are built up on the surface of the conductive layer of the electricaHy conductive elements of compound a) using one of two methods.
  • One is the sol-gel method described in "Stalder and AugustynskiinJ. Electrochem. Soc. 1979, 126:2007” and in Example 1.
  • Another is the “colloidal method” described in Examples 2 and 3.
  • a photosensitiser preferably a photosensitizer dye
  • a photosensitizer dye is applied onto the Ti0 2 .
  • a photosensitizer is a ruthenium, osmium or iron complex or a supramolecular complex of two or three transition metals or a thin layer of iron sulphide (FeS 2 - pyrite).
  • component b) (and b : ) is a charge transfer relay.
  • the charge transfer relays present in the electrolyte transport electric charge from one electrode to the other. Theyact as pure mediators and undergo no chemical alteration during the operation of the cell.
  • component b) (and b j ) is a glassified solid electrolyte, preferably a precious metal salt, more preferably a silver, platinum or gold salt such as halide or borate especially silver iodide or silver borate.
  • a glassified solid electrolyte is a product that can be applied as a fluid that solidifies on further treatment, such as heating.
  • component c) (and c,) has a transparency of at least 60%, more preferably at least 80%, most preferably 80-98%.
  • component c) (and c ) is either
  • ⁇ a composite or blend of a homopolymer or copolymer of an intrinsically conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylene vinylene), poly(p-phenylene sulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine (especially when polyazine it is polyazine doped with halogen eg iodine) and polyaniline; (more preferably polyaniline, polypyrrole or polyacetylene) with up to 60% of a polymer selected from polyamide, polyolefins (polyethylene or polypropylene), polycarbonate and polymethacrylate (hereinafter component ⁇ ) or
  • poly ⁇ cryl ⁇ te and copolymers preferably doped with metallic oxides, preferably with Sn0 2 , A1 2 0 3 and/or ZnO (hereinafter component iii); or
  • component c) (and ) is selected from commercially available electrically conductive polymeric products such as Lutamer P 160 from BASF which is a polymer based on polypyrrole or ICP 275 based on polyaniline from Zipperling or AJmeco Protect from Herikel or Covexal from Cowa in Singen (FRG) which is a polyacrylate and copolymer doped with ZnO (and optionally Sn0 2 ) can also be used.
  • electrically conductive polymeric products such as Lutamer P 160 from BASF which is a polymer based on polypyrrole or ICP 275 based on polyaniline from Zipperling or AJmeco Protect from Herikel or Covexal from Cowa in Singen (FRG) which is a polyacrylate and copolymer doped with ZnO (and optionally Sn0 2 ) can also be used.
  • FSG Cowa in Singen
  • the components a) and c) (and a x and c 1# respectively) may be further doped with halogen e.g. iodine, preferably in an amount of not more than 10%, preferably 2-5% by weight of the component.
  • halogen e.g. iodine
  • component c) when not an intrinsicall ⁇ conductive polymer used in a photovoltaic cell according to the invention is made of tin dioxide doped with ca.0.8 atom percent of fluorine and this layer is deposited on a transparent substrate made of low-cost soda lime float glass.
  • This type of conducting glass can be obtained from Asahi Glass Company, Ltd. Tokyo, Japan, under the brand name of TCO glass.
  • the transparent conductive layer can also be made of indium oxide doped with up to 5% tin oxide, deposited on a glass substrate. This is available from Balzers under the brand name of ITO glass.
  • a photovoltaic cell comprises
  • an electrically conductive element hereinafter the first electrode
  • a solid (preferably glassified) electrolyte preferably based on a precious metal salt (eg silver, gold or platinum halide (eg iodide or bromide)) and
  • an intrinsically conductive polymer herein defined as the second electrode (with no Ti0 2 coating) which contacts the TiO z layer of the first electrode (or the electrolyte if present), whereby there is visible light transmittance through at least the first or second electrode of at least 60%; (preferably also solar light transmittance is at least 60%).
  • the first electrode is a metal, polymer or glass plate substrate to which an electrically conductive surface has been applied,to which one or more layers (preferably a film of 0.1-50 microns) of titanium dioxide has been applied; (preferably the Ti0 2 is coated with a photosensitizer - preferably a transition metal compound e.g. dyestuff).
  • a photosensitizer preferably a transition metal compound e.g. dyestuff
  • both electrodes have a surface resistance of 5-1000 ohm/cms 2 , more preferably 5-100 ohm/cms 2 , most preferably 5-15 ohm/cms 2 , especially 10 ohm/cms 2
  • the intrinsically conductive polymers are selected from components i) and ⁇ ) defined above.
  • the second electrode (also known as “the counterelectrode”) may be coated with a thin layer (preferably up to 10 microns thickness) of an electrccatalyst.
  • the role of the electroc ⁇ t ⁇ lyst is to facilitate the transfer of electrons from the counterelectrode to the electrolyte.
  • a further possible modification is to make one of the electrodes reflect light so that light having passed through the other electrode is reflected back into the cell, from the said one electrode.
  • the first electrode may be supported on a glass, metal or polymer substrate (which polymer may also be selected from those polymers that can be used for component c)).
  • the second electrode is such that the substrate preferably has a visible light transmittance of 60-99%, more preferably 85-95%.
  • the second electrode has a surface resistance of less than 10 ohms per square cm.
  • the first electrode is glass coated with a film of meted oxide, preferably tin oxide (e.g. ITO glass from Fa. Balzars).
  • meted oxide preferably tin oxide (e.g. ITO glass from Fa. Balzars).
  • a photovoltaic cell according to the present invention provides a better overall stability from systems previously known.
  • the photovoltaic coaxial cell may also have the following advantages:
  • the cell will be automatically integrated by a simple and periodic isolatio of the wires; b) the cell avoids the need for conductive wire on the surface of the ce between the modules thereby making it cheaper to make; c) the cell can be produced continuously (eg in a fashion similar to th described in EP 294, 504; for example by passing a cylindrical conductin element through a titanium dioxide colloid or paste followed by drying an sintering at 450 °C . This is followed by optionally (though preferably) dippin the element into a photosensitizer solution followed by drying. The coate element is then passed through molten electrolyte (at elevated temepratur which is then soiidified on the element by cooling.
  • molten electrolyte at elevated temepratur which is then soiidified on the element by cooling.
  • Electrically conductiv polymer is brought into molten state and the coated element is passes conventionally there through and the polymer is cooled to solidify th polymer on the element.
  • the titanium dioxide is dope with a divalent or trivalent metal in an amount of not more than 15% doping b weight based on the amount of Ti0 2 present.
  • the deposition of the pur dopant in the form of a very thin top oxide layer can also be advantageous.
  • blocking layer is formed which impedes leakage current at the electricall conductive element-electrolyte junction.
  • Ti0 2 film can be formed by the sol g process method described in Example 1.
  • the total thickness of the Ti0 2 film is from 5 to 50 microns (more preferably 10-20 microns).
  • a preferred photovoltaic cell is shown in Figure 1..
  • the photovoltaic cell is based on the sensitization of an aluminium, doped titanium dioxide film supported on conducting glass and can be fabricted as follows:
  • a stock solution of organic titanium dioxide precursor is prepared by dissolving 21 mmols of freshly distilled TiCl 4 in 10 m of absolute ethanol. TiCl 4 in the ethanol solution gives titanium alkoxide spontaneously which hydrolyses to give Ti0 2 .
  • the stock solution is then diluted further with absolute ethanol to give two solutions (solution A and solution B) having titanium contents of 25 mg/ml (solution A) and 50 mg/ml (solution B).
  • a third solution (solution C) is prepared from solution B by the addition of A1C1 3 to yield an aluminium content of 1.25 mg/ml.
  • Japan having a surface area of 10 cm 2 and having a visible transmittance of at least 85% and a surface resistance smcdler than 10 ohms per square cm is used as the support on to which to which the Ti0 2 can be deposited as a layer.
  • the glass Prior to deposition, the glass is cleaned with alcohol. A droplet of solution A is spread by use of a doctor blade over the surface of the conducting glass to produce a thin coating. Subsequently the layer is hydrolysed at 28°C for 30 minutes in a special chamber where the humidity is kept at 48% of the equilibrium saturation pressure of water. Thereafter the electrode is heated in air in a tubular oven kept at 450°C, preheating it in the entrance of the oven for 5 minutes followed by 15 minutes of heating in the interior.
  • the film Prior to deposition of the dye, the film is subjected to a sintering treatment in highly purified argon (99.97%). A horizontcd tubular oven is employed. After insertion of the glass sheet with the Ti02 film, the film is twice purged with argon. The glass sheet is then heated under argon flux at a flow rate of 2.5L/h and a temperature gradient of 500°C/h up to 550°C at which temperature it is maintained for 35 minutes. This treatment produces a crystal modification of Ti0 2 , that is an anatase film with a surface roughness factor of 80-200.
  • the glass sheet After cooling under a continuous flow of argon, the glass sheet is immeditaely transferred to an alcoholic solution a chromophore, the chromophore employed being the trimeric ruthenium complex
  • a photovoltaic cell according to the invention is shown in Figure 1. It is constructed, using ⁇ dye (2) coated on a Ti0 2 film (3) supported on an Asahi conducting glass as described above support (4+5) this forming the working electrode (2-5). This is supported on a transparent conductive tin dioxide layer (4) and a glass substrate (5) as a photoanode.
  • the cell has a sandwich-like configuration, the working electrode (2-5) being directly in contact with the counterelecrrode, a transparent polymer (1) (an intrinsically conductive polymer - ICP 275 available from Zipperling or Lutamer P 160 available from BASF) of a thickness of ca. 20 microns.
  • a transparent glass (or ICP transparent polymer) working electrode is an advantage for photovoltaic applications since it allows the harvesting of light from both sides.
  • the working electrode can contain a reflective surface.
  • a transparent Ti0 2 film from colloidal titanium dioxide particles is deposited on an alumina (or conducting glass) support (5) and sintered to yield a coherent highly porous semiconducting film that is transparent and can be used instead of the TiO z layer film in Example 1. This is made as follows:
  • Colloidal titanium oxide particle of approximately lOnm are prepared by hydrolysis of titanium isopropoxide as follows: 125 ml of titanium isopropoxide is added to a solution of 0. IM nitric acid in 750ml of wcrter whilst stirring. A precipitate of amorphous titanium dioxide is formed under these conditions. This is heated to 80°C for approximcrtely 8 hours, stirring vigorously, resulting in peptisation of the precipitate and formation of a clear solution of colloidal anatase. The anatase structure of the titanium dioxide particles is established by Raman spectroscopy.
  • a three layer structure is formed, the lowest being the glass support followed by the 0.5 micron thick fluorine-doped Sn0 2 (the fluorine dopant is less that 5%) and the 2.7 micron thick titanium dioxide layer. It would appear to be a Ti0 2 film composed of a three dimensioned network of interconnected particles having an average size of approximately 16nm. Apparently, significant particle growth occurs during sintering.
  • a copolymer based on 70% polyamide and 30% polyaniline is melted at 300°C and is applied by a squeegee (or doctor blade) spreading a sheet of polymer over the ruthenium complex surface to a thickness of 20 microns.
  • the fined thickness of the titanium dioxide film is 5 microns.
  • the film is fired for 1 hour at 250°C .
  • the coating of Ti0 2 with dyestuff is performed by immersing the plastics sheet for 16 hours in an ethanolic solution containing the trimeric ruthenium complex RuL 2 (CNRuL' 2 CN) 2 where L stand for 2,2-bipyridyl 4,4'-dicarboxylate and L' stands for 2,2'-bipyridyl.
  • the plastics sheet displays an intensive dark red coloration. Due to the high concentration of dyestuff, the porous film is capable of harvesting photons over a very broad spectral range extending from 400 to 750 nm.
  • the plastics sheet is cut into two parts each having a s ⁇ e of ca 9 c 2 m. These sheets serve as working electrodes (photo-anodes) in the module whose ossembly is described further below.
  • Transparent counterelecfrodes are made of the same type of polymer as the working electrodes, except the counterelectrcde is not coated with Ti0 2 .
  • a photovoltaic ceU which is a modification of the ced of Figure I, as shown in Figure 3 and can be made up as described in Example 1 in which the counter electrode and the working electrode are the same.
  • the working electrode comprises titantium dioxide layer 3 to which dye 2 has been applied, supported on an Asahi conducting glass support (4+5) comprising a transparent conductive tin dioxide layer (4) and a glass substrate (5).
  • the counter electrode is an Asahi conducting glass support (7 and 8) comprising a transparent conductive tin dioxide layer (7) and a glass substrate (8). These glass supports are made according to the method of Example 1.
  • a solid electrolyte (6) of 20 microns separates the working elecrode (4,5) from the counterelectrcde (7,8).
  • FIG. 4 A further embodiment of a photovoltaic ced according to the invention can be seen in Figure 4, in which a conductive wire such as copper (11) supports a layer of Ti0 2 (13) coated with dyestuff (12) on its outer surface and surrounded by a intrinsiccdLy conductive polymer (ICP 275 or Lutamer P 160 of Example 1) (14) as the counterelectrcde.
  • a conductive wire such as copper (11) supports a layer of Ti0 2 (13) coated with dyestuff (12) on its outer surface and surrounded by a intrinsiccdLy conductive polymer (ICP 275 or Lutamer P 160 of Example 1) (14) as the counterelectrcde.
  • the wire can be coated with Ti0 2 by a method as described in Example III of EP 294504 by drawing it though a solution of Ti0 2 as described in Example 1 of EP 294 504.
  • Coating with dyestuff is carried out by drawing the TiO z coated wire through a dyestuff solution (of the dye of Example 1 of the present application).
  • Coating with an intrinsiccdLy conductive polymer is carried out by drawing the wire through ⁇ melt of the polymer. The amount of chemical taken up can be regulated by the rate of drawing the wire through the appropriate solution and the tempercrture of the solution.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

New TiO2 containing photovoltaic cells effective in the conversion of visible light to electric energy as follows: a photovoltaic cell comprising: a) an electrically conductive element to which one or more titanium dioxide layers have been applied (hereinafter component a); b) a solid electrolyte (hereinafter component b); and/or c) an electrically conductive element through which light can pass to the TiO2 layer (hereinafter component c).

Description

PHOTOVOLTAIC CELLS
The invention relates to new Ti02 containing photovoltaic cells effective in the conversion of visible light to electric energy.
According to the invention there is provided a photovoltaic cell comprising:
a) an electrically conductive element on to which one or more titanium dioxide layers have been applied (hereinafter component a);
b) a solid electrolyte (hereinafter component b); and/or
c) an electrically conductive element through which light can pass to the Ti02 layer (hereinafter component c).
Further according to the invention there is provided a photovoltaic cell (hereinafter the photovoltaic coaxial cell) comprising
a) a cylindrical conductive element (eg a textile conductive filament or a wire such as copper wire) on to which one or more titanium dioxide layers have been applied (hereinafter component x):
b) a solid electrolyte that has been applied concentrically around the cy-tad-rical component a, (hereinafter component bj); and/or
c) an electrically conductive element through which light can pass to the Ti02 layer, that has been applied concentrically around the cylindrical component a, (hereinafter component cλ . Preferably component a) comprises a support, (preferably a glass plate coated with metal oxide, a metal surface or a polymer sheet (preferably an intrinsically conductive polymer)) to which the Ti02 layer is applied. Optionally, component a) is transparent. By the term "transparent" is meant that at least 60%, preferably 70%, more preferably at least 80%, especially 80-98% of incident light passes through the glass.
Preferably the Ti02 layer comprises rutile and anatase, more preferably anatase.
Preferably the titanium dioxide is doped with a metal ion, which may be selected from a divalent or trivalent metal or boron. Preferred dopant is aluminium.
Preferably the titanium dioxide layer is a film. Preferably the film has a roughness factor greater than 20, the roughness factor being defined as the ratio of true to apparent surface area. Roughness factor is defined in USP 5,084,365 and 4,927 , 721. More preferably the roughness factor is 20- 000 , most preferably 50-200.
Preferably the titanium dioxide layers are built up on the surface of the conductive layer of the electricaHy conductive elements of compound a) using one of two methods. One is the sol-gel method described in "Stalder and AugustynskiinJ. Electrochem. Soc. 1979, 126:2007" and in Example 1. Another is the "colloidal method" described in Examples 2 and 3.
Preferably in a photovoltaic cell or a photovoltaic coaxial cell according to the invention, a photosensitiser (preferably a photosensitizer dye) is applied onto the Ti02. Preferably such a photosensitizer is a ruthenium, osmium or iron complex or a supramolecular complex of two or three transition metals or a thin layer of iron sulphide (FeS2 - pyrite). Preferably component b) (and b:) is a charge transfer relay. The charge transfer relays present in the electrolyte transport electric charge from one electrode to the other. Theyact as pure mediators and undergo no chemical alteration during the operation of the cell. More preferably component b) (and bj) is a glassified solid electrolyte, preferably a precious metal salt, more preferably a silver, platinum or gold salt such as halide or borate especially silver iodide or silver borate. What is meant by a glassified solid electrolyte is a product that can be applied as a fluid that solidifies on further treatment, such as heating.
Preferably component c) (and c,) has a transparency of at least 60%, more preferably at least 80%, most preferably 80-98%.
Preferably component c) (and c ) is either
i) an intrinsically conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), poly-(p- phenylenesulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine (especially when polyazine it is polyazine doped with halogen eg iodine) and polyaniline; (more preferably polyaniline, polypyrrole or polyacetylene) (hereinafter component i); or
ϋ) a composite or blend of a homopolymer or copolymer of an intrinsically conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylene vinylene), poly(p-phenylene sulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine (especially when polyazine it is polyazine doped with halogen eg iodine) and polyaniline; (more preferably polyaniline, polypyrrole or polyacetylene) with up to 60% of a polymer selected from polyamide, polyolefins (polyethylene or polypropylene), polycarbonate and polymethacrylate (hereinafter component ϋ) or
iii) polyαcrylαte and copolymers preferably doped with metallic oxides, preferably with Sn02, A1203 and/or ZnO (hereinafter component iii); or
a mixture of components i, ϋ and/or iii.
Preferably component c) (and ) is selected from commercially available electrically conductive polymeric products such as Lutamer P 160 from BASF which is a polymer based on polypyrrole or ICP 275 based on polyaniline from Zipperling or AJmeco Protect from Herikel or Covexal from Cowa in Singen (FRG) which is a polyacrylate and copolymer doped with ZnO (and optionally Sn02) can also be used. Such polymers are described in the article "Tapping the power of intrinsic conductivity" A. Stuart Wood in Modem Plastics August 1991, the contents of which is incorporated herein by reference.
The components a) and c) (and ax and c1# respectively) may be further doped with halogen e.g. iodine, preferably in an amount of not more than 10%, preferably 2-5% by weight of the component.
Preferably component c) when not an intrinsicallγ conductive polymer used in a photovoltaic cell according to the invention is made of tin dioxide doped with ca.0.8 atom percent of fluorine and this layer is deposited on a transparent substrate made of low-cost soda lime float glass. This type of conducting glass can be obtained from Asahi Glass Company, Ltd. Tokyo, Japan, under the brand name of TCO glass. The transparent conductive layer can also be made of indium oxide doped with up to 5% tin oxide, deposited on a glass substrate. This is available from Balzers under the brand name of ITO glass. Further according to the invention a photovoltaic cell comprises
a) an electrically conductive element (hereinafter the first electrode);
b) optionally (though preferably) a solid (preferably glassified) electrolyte preferably based on a precious metal salt (eg silver, gold or platinum halide (eg iodide or bromide)) and
c) an intrinsically conductive polymer (herein defined as the second electrode) (with no Ti02 coating) which contacts the TiOz layer of the first electrode (or the electrolyte if present), whereby there is visible light transmittance through at least the first or second electrode of at least 60%; (preferably also solar light transmittance is at least 60%).
Preferably the first electrode is a metal, polymer or glass plate substrate to which an electrically conductive surface has been applied,to which one or more layers (preferably a film of 0.1-50 microns) of titanium dioxide has been applied; (preferably the Ti02 is coated with a photosensitizer - preferably a transition metal compound e.g. dyestuff).
Preferably both electrodes have a surface resistance of 5-1000 ohm/cms2, more preferably 5-100 ohm/cms2, most preferably 5-15 ohm/cms2, especially 10 ohm/cms2
Preferably the intrinsically conductive polymers are selected from components i) and ϋ) defined above.
The second electrode (also known as "the counterelectrode") may be coated with a thin layer (preferably up to 10 microns thickness) of an electrccatalyst. The role of the electrocαtαlyst is to facilitate the transfer of electrons from the counterelectrode to the electrolyte.
A further possible modification is to make one of the electrodes reflect light so that light having passed through the other electrode is reflected back into the cell, from the said one electrode.
The first electrode may be supported on a glass, metal or polymer substrate (which polymer may also be selected from those polymers that can be used for component c)).
Optionally (though preferably) the second electrode is such that the substrate preferably has a visible light transmittance of 60-99%, more preferably 85-95%. Preferably the second electrode has a surface resistance of less than 10 ohms per square cm.
Preferably the first electrode is glass coated with a film of meted oxide, preferably tin oxide (e.g. ITO glass from Fa. Balzars).
Photovoltaic cells according to the invention have advantages selected from the following:
1. Where solid electrolyte is present, the use of fluid electrolyte is avoided. This brings a good long term light fastness and avoids the drawback associated with cells having fluid electrolyte of deteriorcrtion of the first electrode and avoids deterioration of the electrodes of the integrated cells.
2. A photovoltaic cell according to the present invention provides a better overall stability from systems previously known.
3. With this system, it will be possible to build very thin and flexible solar cells that could be adapted easily to any form. 4. The photovoltaic coaxial cell may also have the following advantages:
a) the cell will be automatically integrated by a simple and periodic isolatio of the wires; b) the cell avoids the need for conductive wire on the surface of the ce between the modules thereby making it cheaper to make; c) the cell can be produced continuously (eg in a fashion similar to th described in EP 294, 504; for example by passing a cylindrical conductin element through a titanium dioxide colloid or paste followed by drying an sintering at 450 °C . This is followed by optionally (though preferably) dippin the element into a photosensitizer solution followed by drying. The coate element is then passed through molten electrolyte (at elevated temepratur which is then soiidified on the element by cooling. Electrically conductiv polymer is brought into molten state and the coated element is passe conventionally there through and the polymer is cooled to solidify th polymer on the element. In order to increase the voltage "gridding" carried out conventionally); d) there is increased use for the cell due to its adaptability to any surface; e) it may be a more efficient cell; and f) it may have improved heat dissipation.
For producing the electrically conductive element or first electrode with Ti applied by the sol gel method it is preferable that the titanium dioxide is dope with a divalent or trivalent metal in an amount of not more than 15% doping b weight based on the amount of Ti02 present. However, the deposition of the pur dopant in the form of a very thin top oxide layer can also be advantageous. blocking layer is formed which impedes leakage current at the electricall conductive element-electrolyte junction. Ti02 film can be formed by the sol g process method described in Example 1. Preferably the total thickness of the Ti02 film is from 5 to 50 microns (more preferably 10-20 microns).
The photosensitising layer may be produced by applying to the lϊ02 layer a dye according to the invention defined for example in WO 91/ 16719 (=PCT/EP 91/00734) (Graetzel) the content of which is incorporated herein by reference. Especially incorporated herein by reference are the dyes set out in WO 91/16719.
The invention will now be illustrated by the following Examples.
In the Figures that follow, where elements are the same in each Figure the same numbering is used. The number (2) for exmaple in Figures 1-4 refers to the same element, i.e. the photosensitizer dye.
light photon in each Figure are referred to as 9.
Example 1
A preferred photovoltaic cell is shown in Figure 1..
The photovoltaic cell is based on the sensitization of an aluminium, doped titanium dioxide film supported on conducting glass and can be fabricted as follows:
A stock solution of organic titanium dioxide precursor is prepared by dissolving 21 mmols of freshly distilled TiCl4 in 10 m of absolute ethanol. TiCl4 in the ethanol solution gives titanium alkoxide spontaneously which hydrolyses to give Ti02. The stock solution is then diluted further with absolute ethanol to give two solutions (solution A and solution B) having titanium contents of 25 mg/ml (solution A) and 50 mg/ml (solution B). A third solution (solution C) is prepared from solution B by the addition of A1C13 to yield an aluminium content of 1.25 mg/ml. A conducting glass sheet from Asahi Inc. Japan having a surface area of 10 cm2 and having a visible transmittance of at least 85% and a surface resistance smcdler than 10 ohms per square cm is used as the support on to which to which the Ti02 can be deposited as a layer. Prior to deposition, the glass is cleaned with alcohol. A droplet of solution A is spread by use of a doctor blade over the surface of the conducting glass to produce a thin coating. Subsequently the layer is hydrolysed at 28°C for 30 minutes in a special chamber where the humidity is kept at 48% of the equilibrium saturation pressure of water. Thereafter the electrode is heated in air in a tubular oven kept at 450°C, preheating it in the entrance of the oven for 5 minutes followed by 15 minutes of heating in the interior. Three more layers are produced in the same way. Subsequently, 5 thicker layers are deposited by using solution B. The same procedure as for the first layers is applied. Finally solution C is used to deposit the last two layers contciining the aluminium dopant. The heating of the last layer in the tubular oven is extended from 15 to 30 minutes. The toted thickness of the titanium dioxide film is between 10 and 20 microns.
Prior to deposition of the dye, the film is subjected to a sintering treatment in highly purified argon (99.97%). A horizontcd tubular oven is employed. After insertion of the glass sheet with the Ti02 film, the film is twice purged with argon. The glass sheet is then heated under argon flux at a flow rate of 2.5L/h and a temperature gradient of 500°C/h up to 550°C at which temperature it is maintained for 35 minutes. This treatment produces a crystal modification of Ti02, that is an anatase film with a surface roughness factor of 80-200.
After cooling under a continuous flow of argon, the glass sheet is immeditaely transferred to an alcoholic solution a chromophore, the chromophore employed being the trimeric ruthenium complex
[Ru(L2)[(CN)2RuL'2]2]
where L is 2,2TDipyridyl-4,4'-dicarboxylic acid and U is 2,2'-bipyridyl. Its concentration in absolute alcohol is δXlO^M. Prolonged exposure of the film to the open air prior to dye absorption is avoided in order to prevent hydroxylation of the Ti02 surface as the presence of hydroxy groups at the electrode surface interferes with the dye uptake. The adsorption of chromophore from the ethanolic solution is allowed to continue for 30 minutes after which time the glass sheet is withdrawn and washed briefly with absolute ethanol. The Ti02 layer on the sheet assumes a deep red colour because of the chromophore coating.
A photovoltaic cell according to the invention is shown in Figure 1. It is constructed, using α dye (2) coated on a Ti02 film (3) supported on an Asahi conducting glass as described above support (4+5) this forming the working electrode (2-5). This is supported on a transparent conductive tin dioxide layer (4) and a glass substrate (5) as a photoanode. The cell has a sandwich-like configuration, the working electrode (2-5) being directly in contact with the counterelecrrode, a transparent polymer (1) (an intrinsically conductive polymer - ICP 275 available from Zipperling or Lutamer P 160 available from BASF) of a thickness of ca. 20 microns.
A transparent glass (or ICP transparent polymer) working electrode is an advantage for photovoltaic applications since it allows the harvesting of light from both sides. Alterncrtively, the working electrode can contain a reflective surface.
Alternatively, a modification to the cell of Figure 1 is shown in Figure 2. This differs from Figure 1 by the presence of a solid state electrolyte (6), which is a thin (20 microns) layer of 'silver iodide, located between the working electrode (2-5) and the counter electrode (1).
Example 2
A transparent Ti02 film from colloidal titanium dioxide particles is deposited on an alumina (or conducting glass) support (5) and sintered to yield a coherent highly porous semiconducting film that is transparent and can be used instead of the TiOz layer film in Example 1.This is made as follows:
Colloidal titanium oxide particle of approximately lOnm are prepared by hydrolysis of titanium isopropoxide as follows: 125 ml of titanium isopropoxide is added to a solution of 0. IM nitric acid in 750ml of wcrter whilst stirring. A precipitate of amorphous titanium dioxide is formed under these conditions. This is heated to 80°C for approximcrtely 8 hours, stirring vigorously, resulting in peptisation of the precipitate and formation of a clear solution of colloidal anatase. The anatase structure of the titanium dioxide particles is established by Raman spectroscopy. The sol is concentrated by evaporation of the solvent in vacuum crt room temperature until a viscous licjuid is obtained contcπning the colloidcd particles. At this stage the nonionic surfactant TRITON X-100 (commericcdly available from Rohm & Hass) in any amount of 40% weight of Ti02 is added to reduce cracking of the film when applied to a substrate.
The titanium dioxide films are formed by spin coating the concentrated sol on to a conducting glass substrate. Usually it is sufficient to apply 6 to 10 layers in order to obtain semiconductor membranes of sufficient surface area to give excellent visible light harvesting efficiencies after deposition of a monolayer of the sensitizer.
A three layer structure is formed, the lowest being the glass support followed by the 0.5 micron thick fluorine-doped Sn02 (the fluorine dopant is less that 5%) and the 2.7 micron thick titanium dioxide layer. It would appear to be a Ti02 film composed of a three dimensioned network of interconnected particles having an average size of approximately 16nm. Apparently, significant particle growth occurs during sintering.
The transparent Ti02 films are tested in conjunction with a sensitizer, Ru L3 where L is 2,2'bipyridyl-4,4'dicarboxylic acid regenerative cell for the generation of electricity from visible light. The results can be represented where the photocurrent under simulated sunlight (intensity ca 30W/m2) is plotted as a function of cell voltage.
A copolymer based on 70% polyamide and 30% polyaniline is melted at 300°C and is applied by a squeegee (or doctor blade) spreading a sheet of polymer over the ruthenium complex surface to a thickness of 20 microns.
Example 3
A sheet of plastics (Lutamer PI 60 - BASF - a polypyrrole polymer) having a size of 2x9.6 cm2 is coated with a colloidal titanium dioxide film according to the procedure of Example 2. A total of 7 layers of Ti02 colloid are deposited successively by spin coating and the film is subjected each time to a temperature of 200°C for 30 minutes. 30% (w/w) of TRITON X 405 surfactant is added in order to avoid cracking of the film.
The fined thickness of the titanium dioxide film is 5 microns.
Immediately before coating with dye-stuff, the film is fired for 1 hour at 250°C . The coating of Ti02 with dyestuff is performed by immersing the plastics sheet for 16 hours in an ethanolic solution containing the trimeric ruthenium complex RuL2(CNRuL'2CN)2 where L stand for 2,2-bipyridyl 4,4'-dicarboxylate and L' stands for 2,2'-bipyridyl. After coating, the plastics sheet displays an intensive dark red coloration. Due to the high concentration of dyestuff, the porous film is capable of harvesting photons over a very broad spectral range extending from 400 to 750 nm.
After dye deposition, the plastics sheet is cut into two parts each having a s^e of ca 9 c2m. These sheets serve as working electrodes (photo-anodes) in the module whose ossembly is described further below. Transparent counterelecfrodes are made of the same type of polymer as the working electrodes, except the counterelectrcde is not coated with Ti02.
Example 4
A photovoltaic ceU which is a modification of the ced of Figure I, as shown in Figure 3 and can be made up as described in Example 1 in which the counter electrode and the working electrode are the same. The working electrode comprises titantium dioxide layer 3 to which dye 2 has been applied, supported on an Asahi conducting glass support (4+5) comprising a transparent conductive tin dioxide layer (4) and a glass substrate (5). The counter electrode is an Asahi conducting glass support (7 and 8) comprising a transparent conductive tin dioxide layer (7) and a glass substrate (8). These glass supports are made according to the method of Example 1. A solid electrolyte (6) of 20 microns separates the working elecrode (4,5) from the counterelectrcde (7,8).
Example 5
A further embodiment of a photovoltaic ced according to the invention can be seen in Figure 4, in which a conductive wire such as copper (11) supports a layer of Ti02 (13) coated with dyestuff (12) on its outer surface and surrounded by a intrinsiccdLy conductive polymer (ICP 275 or Lutamer P 160 of Example 1) (14) as the counterelectrcde.
The wire can be coated with Ti02 by a method as described in Example III of EP 294504 by drawing it though a solution of Ti02 as described in Example 1 of EP 294 504. Coating with dyestuff is carried out by drawing the TiOz coated wire through a dyestuff solution (of the dye of Example 1 of the present application). Coating with an intrinsiccdLy conductive polymer is carried out by drawing the wire through α melt of the polymer. The amount of chemical taken up can be regulated by the rate of drawing the wire through the appropriate solution and the tempercrture of the solution.
The complexes of the other compounds of Examples 1 to 33 of PCT/EP91/ 00734 can be used in place of the ruthenium complexes of Examples 1 to 5 in the photovoltaic ced. These components are shown in Figure l below.
Table 1
Figure imgf000017_0001
in which 'bpy" = 2,2' - bipyridyl "Me" = methyl "ph" = phenyl Examples 9-33 of PCT/EP 91/00734
By a method analogous to that of Example 1, complexes as defined in Table 2 can be prepared from suitable reactants.
In Table 2 below, bpy = 2,2' bipyridyl; biq = 2,2' biquinoline and phen = 1,10 phenanthroline in compounds, 19 2-phenylpyridine is used in compound 22 straight and branched alkyl groups are used in compound 26 N,N-tetramed yl and C,C - tetramethyl ethylene diamine are used in compound 27 2,2' bis(diphenylphoφhino)-l,l'bincιphthγlene is used in compound 28, 30 and 33 1,10 orthophenanthrolene is used and in compound 31 4-(2-pyridyl) azo resorcinol is used
Table 2
Figure imgf000019_0001
Figure imgf000020_0001

Claims

Clcrims:
1. A photovoltaic ceU comprising:
a) an electriccdly conductive element to which one or more titanium dioxide layers have been applied (hereinafter component a); b) a solid electrolyte (hereinafter component b); and/or c) an electriccdly conductive element through which light can pass to the Ti02 layer (hereinafter component c).
2. A photovoltaic ceU (hereinafter the photovoltaic coaxicd ceU) comprising
a) a cylindrical conductive element (eg a textile conductive filament or a wire such as copper wire) on to which one or more titanium dioxide layers have been applied (hereinafter component aλ) b) a solid electrolyte that has been applied concentriccdly around the cylindriccd component a, (hereinafter component bL); and/or c) a light fransmitting electriccdly conductive polymer, through which light can pass to the Ti02 layer, thcrt has been applied concentriccdly around the cylindriccd component ax (hereinafter component Cj).
3. A ced according to Claim 1 or Claim 2 in which the titanium dioxide film has a roughness factor greater than 20, the roughness factor being defined as the ratio of true to apparent surface area.
4. A ced according to any one of the preceeding claims in which a photosensitiser is applied to the Ti02 layer.
5. A ced according to any one of the preceding claims in which component b) is a glassified solid electrolyte
6. A ced according to any one of the preceeding claims in which component c) is either
i) an intrinsiccdly conductive polymer based on a polymer selected from polyacetylene, polγ(p-phenylene), poly(p-phenylenevinylene), poly(p- phenylenesulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine and polyaniline; (hereinafter component i) or
ii) a composite or blend of a homopolymer or copolymer of an intrinsiccdly conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), poly(p-phenylene sulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine (including polyazine doped with halogen eg iodine) and polyaniline; with up to 60% of a polymer selected from polyamide, polyolefins, polycarbonate and polymethacrylcrte (hereinafter component ii) or
iii) polyacrylate and copolymers thereof (hereinafter component iii); or
a mixture of components i, ii and/or iii.
7. A photovoltaic ced comprising
a) an electriccdly conductive element (hereinafter the first electrode); b) optioncdly a solid electrolyte; and c) an mtrinsiccdly conductive polymer (hereinafter the second electrode) (with no Ti02 coating) which contacts the Ti02 layer of the first electrode (or the electrolyte if present), whereby the visible light transmittance of at least the polymer is at least 60%.
8 A ced according to Claim 7 in which the intrinsiccdly conductive polymer is selected from components i) and ii).
i) cm intrinsiccdly conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), poly(p- phenylenesulphide), polypyrrole, polythiophene, polyfurcme, polyazulene, polyazine and polyaniline; (hereinafter component i) or
n) a composite or blend of a homopolymer or copolymer of an intrinsiccύly conductive polymer based on a polymer selected from polyacetylene, poly(p-phenylene), poly(p-phenylenevinylene), poly(p-phenylene sulphide), polypyrrole, polythiophene, polyfurane, polyazulene, polyazine (including polyazine doped with halogen eg iodine) and polyaniline; with up to 60% of a polymer selected from polyamide, polyolefins, polycarbonate and polymethacrylate (hereinafter component ii).
9. A photovoltaic ced substanticdly as herein described with reference to any one of Examples 1 to 5.
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WO2003107471A1 (en) 2002-06-14 2003-12-24 日立マクセル株式会社 Photoelectric transducer and its manufacturing method
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WO2004097871A3 (en) * 2003-04-30 2005-08-11 Ecole Polytech Dye sensitized solar cell
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EP2204875A1 (en) * 2003-05-30 2010-07-07 Fujikura, Ltd. Electrolyte composition and photoelectric conversion element using same
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US9196847B2 (en) 2005-12-23 2015-11-24 Commissariat A L'energie Atomique Sensitizing complexes, process for the preparation thereof, semiconductive inorganic/organic hybrid material comprising them, and photovoltaic cell comprising said material
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US10734165B2 (en) 2015-10-02 2020-08-04 Alliance For Sustainable Energy, Llc Heterojunction perovskite photovoltaic devices and methods of making the same
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