US20060243587A1 - Photoelectrochemical device - Google Patents
Photoelectrochemical device Download PDFInfo
- Publication number
- US20060243587A1 US20060243587A1 US10/555,867 US55586705A US2006243587A1 US 20060243587 A1 US20060243587 A1 US 20060243587A1 US 55586705 A US55586705 A US 55586705A US 2006243587 A1 US2006243587 A1 US 2006243587A1
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- metallic
- photoelectrochemical
- photoelectrochemical device
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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
-
- 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
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2081—Serial interconnection of 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
- Y02E10/542—Dye sensitized solar cells
Definitions
- This invention relates to photovoltaic (PV) devices and more particularly, but not exclusively, to photoelectrochemical photovoltaic devices.
- this invention relates to methods of manufacturing such devices.
- photovoltaic devices are available for conversion of energy of electromagnetic radiation to electrical energy. These include a conventional solid-state devices (see M. Green Third generation photovoltaics: concepts for high efficiency at low cost, The Electrochemical Society Proceedings, Vol. 2001-10, p. 3-18) and more recently developed photoelectrochemical (PEC) devices
- Photoelectrochemical devices as of the type disclosed in the above patents, are capable of being fabricated in a laminate arrangement between two large area substrates.
- One typical arrangement involves two glass substrates, each utilising an electrically conducting coating upon the internal surface of the substrate.
- At least one of said first and second substrates is substantially transparent to visible light, as is the attached transparent electrically conducting (TEC) coating.
- TEC transparent electrically conducting
- PEC cells contain a working electrode, typically comprising a dye-sensitised, nanoporous semiconducting oxide (e.g., titanium dioxide known as titania) layer attached to one conductive coating, and a counter electrode, typically comprising a redox electrocatalyst layer attached to the other conductive coating.
- a working electrode typically comprising a dye-sensitised, nanoporous semiconducting oxide (e.g., titanium dioxide known as titania) layer attached to one conductive coating
- a counter electrode typically comprising a redox electrocatalyst layer attached to the other conductive coating.
- An electrolyte containing a redox mediator is located between the photoanode and cathode, and the electrolyte is sealed from the environment.
- the TEC coatings which usually comprise a metal oxide(s)
- the photoelectrochemical cells are connected in series, internally within a single module.
- Metallic conductors are used for such interconnection.
- choice of metallic conductors is limited to platinum and similar metals, titanium and tungsten because of chemical interactions with the typical iodide containing electrolyte of a photoelectrochemical cell.
- the invention provides for using layers of electrically conductive but chemically inert materials (e.g. diamond and electrically conducting nitrides and carbides) layers to conduct electrical current inside photoelectrochemical cell while protecting metallic components of the photoelectrochemical cell. It has been discovered that thin layers of these materials provide sufficient conductivity to electrically connect highly conductive metallic components, at the same time these materials are chemically inert towards electrolytes utilised in PEC.
- the electrical conductivity of the protecting layer can be modified by variation of composition or thickness so that the layer can be optimised for different applications (e.g., light conditions).
- the protective layers could be deposited using any known technology for their formation (e.g., arc deposition, sol-gel, sputtering, CVD, etc.).
- the layer is required to be sufficiently electrically conductive to enable viable electrical output while being chemically inert toward components of the photoelectrochemical cell.
- the invention also provides for these layers being formed directly on substrate (glass, polymeric materials) without an intermediate metallic component, when requirement for electrical conductance are not high (e.g., —for low light conditions or small cell size).
- This invention is based on realisation that some materials such as titanium nitride form pinhole free strongly bound coatings that protect metallic conductors and, at the same time, provide electrical conductivity sufficient for successful operation of PEC device.
- Our experiments demonstrated that although unprotected 316 stainless steel substrate corrodes within several days of operation at room temperature, causing irreversible damage to electrolyte of the PEC device, a thin and dense layer of TiN coating deposited on the same substrate ensures many months of successful operations at 75° C.
- These include: diamond and semimetallic, metallic (and multimetal) nitrides, carbides, oxides, borides, phosphides, silicides, antimon ides, arsen ides, tellurides and combinations thereof (e.g oxynitrides, arsenide sulphides).
- Still preferred materials for the purpose of this invention are: titanium nitride (TiN), zirconium nitride and boron carbide.
- Further preferred materials include silicides of niobium, molybdenum, tantalum, tungsten or vanadium.
- a TiN layer is deposited on metal foil or plate (e.g., stainless steel foil), thus protecting the foil from electrolyte of the cell.
- metal foil or plate e.g., stainless steel foil
- the foil or plate serves as a substrate for either working or counter electrode of the photoelectrochemical cell.
- a TiN layer is deposited on metallic mesh, used to conduct electrical current generated locally inside a cell to the external terminals.
- the mesh could be used in either or both working or/and counter electrodes of a photoelectrochemical cell.
- a TiN layer is deposited on metallic conductor used to interconnect photoelectrochemical cells in a series connected module.
- metallic conductor used to interconnect photoelectrochemical cells in a series connected module.
- both the working electrode and the counter electrode are divided each into electrically isolated portions, and the said metallic conductor connects at least one portion of the working electrode to a portion of the counter electrode
- FIG. 1 is an enlarged cross sectional view of a PEC device formed in accordance with one example of the invention.
- FIG. 2A is an enlarged cross sectional of a PEC device formed in accordance with another example of the invention.
- FIG. 2B is a diagrammatic view of a stainless steel mesh protected by a TiN coating.
- FIG. 3 is an enlarged cross sectional of a PEC device formed in accordance with further example of the invention.
- the working electrode substrate comprises Stainless Steel foil 1 protected by TiN coating 2 .
- Working electrode 3 (dye sensitised TiO 2 ) formed on TiN coating (3 microns thick, filtered plasma deposition).
- the counter electrode 5 (thin dispersed Pt catalytic layer) of the device is formed on transparent electrically conductive substrate 6 (polymeric film coated by TEC).
- Electrolyte 4 is placed between the two electrodes.
- the device is sealed by silicone based sealant 7 .
- This device is to be illuminated from the counter electrode side.
- a stainless steel foil 1 protected by TiN coating 2 supports counter electrode 5 of a PEC device.
- the working electrode is supported by a transparent electrically conductive substrate 6 , to which a stainless steel mesh 8 coated by TiN 2 is attached.
- the said stainless steel mesh enhances electrical connection to a working electrode 3 (dye sensitised TiO 2 ).
- the device is sealed by silicone based sealant 7 . This device is to be illuminated from the working electrode side.
- the stainless steel mesh 8 ( 50 m aperture, 30 m wire) is protected by a TiN coating 2 .
- a PEC device is formed between two transparent substrates 6 .
- Each substrate is coated by a transparent electronic conductor 9 (TEC, F-doped tin oxide).
- Isolation lines 10 in TEC created with aid of laser radiation divide each electrode into small portions.
- the working electrode substrate is coated by dye sensitised TiO 2 layer 3 and counter electrode substrate—by a catalytic layer 5 , 3 independent cells are formed by filling spaces between the electrode with an electrolyte 4 .
- a conductor is used to connect the cells in series.
- the conductor comprises stainless steel core 11 protected by a TiN coating 12 .
Abstract
Description
- This application is a national stage completion of PCT/AU2004/000590 filed May 5, 2004 which claims priority from Australian Application Serial No. 2003902117 filed May 5, 2003.
- This invention relates to photovoltaic (PV) devices and more particularly, but not exclusively, to photoelectrochemical photovoltaic devices.
- Further, this invention relates to methods of manufacturing such devices.
- A variety of photovoltaic devices are available for conversion of energy of electromagnetic radiation to electrical energy. These include a conventional solid-state devices (see M. Green Third generation photovoltaics: concepts for high efficiency at low cost, The Electrochemical Society Proceedings, Vol. 2001-10, p. 3-18) and more recently developed photoelectrochemical (PEC) devices
- Examples of the PEC cells of the type concerned are disclosed in the following US patents:
- U.S. Pat. No. 4,927,721, Photoelectrochemical cell; Michael Graetzel and Paul Liska, 1990.
- U.S. Pat. No. 5,525,440, Method of manufacture of photo-electrochemical cell and a cell made by this method; Andreas Kay, Michael Graetzel and Brian O'Regan, 1996.
- U.S. Pat. No. 6,297,900, Electrophotochromic Smart Windows and Methods, G. E. Tulloch and I. L. Skryabin, 1997.
- U.S. Pat. No. 6,555,741, Methods to implement interconnects in multi-cell regenerative photovoltaic photoelectrochemical devices, J. A. Hopkins, G. Phani, I. L. Skryabin, 1999.
- U.S. Pat. No. 6,652,904, Methods to manufacture single cell and multi-cell regenerative photoelectrochemical devices, J. A. Hopkins, D. Vittorio, G. Phani, 1999.
- Photoelectrochemical devices, as of the type disclosed in the above patents, are capable of being fabricated in a laminate arrangement between two large area substrates. One typical arrangement involves two glass substrates, each utilising an electrically conducting coating upon the internal surface of the substrate.
- At least one of said first and second substrates is substantially transparent to visible light, as is the attached transparent electrically conducting (TEC) coating.
- PEC cells contain a working electrode, typically comprising a dye-sensitised, nanoporous semiconducting oxide (e.g., titanium dioxide known as titania) layer attached to one conductive coating, and a counter electrode, typically comprising a redox electrocatalyst layer attached to the other conductive coating. An electrolyte containing a redox mediator is located between the photoanode and cathode, and the electrolyte is sealed from the environment.
- Many photoelectrochemical devices would be advantaged by an increased size of the modules. However, the TEC coatings, which usually comprise a metal oxide(s), have high resistivity when compared with normal metal conductors, resulting in high resistive losses for large area photoelectrochemical cells, which affects the efficiency of the device especially in high illumination conditions.
- Electrical resistance of substrates can be reduced by using metal plates, foils or metal mesh. Most of metals commonly used, however, are chemically reactive with the electrolyte of the photoelectrochemical cells. Corrosion of metallic components of PEC cells had been recognised as a major limitation to successful commercialisation of PEC devices for many years.
- In one arrangement the photoelectrochemical cells are connected in series, internally within a single module. Metallic conductors are used for such interconnection. Once again, choice of metallic conductors is limited to platinum and similar metals, titanium and tungsten because of chemical interactions with the typical iodide containing electrolyte of a photoelectrochemical cell.
- It is therefore an object of the present invention to provide a protective coating for low cost metallic conductors used in the photoelectrochemical cells that will solve the combined problem of effective corrosion resistance without loss of effective performance while still being cost effective.
- In accomplishing theforegoing and related objectives, the invention provides for using layers of electrically conductive but chemically inert materials (e.g. diamond and electrically conducting nitrides and carbides) layers to conduct electrical current inside photoelectrochemical cell while protecting metallic components of the photoelectrochemical cell. It has been discovered that thin layers of these materials provide sufficient conductivity to electrically connect highly conductive metallic components, at the same time these materials are chemically inert towards electrolytes utilised in PEC. The electrical conductivity of the protecting layer can be modified by variation of composition or thickness so that the layer can be optimised for different applications (e.g., light conditions).
- The protective layers could be deposited using any known technology for their formation (e.g., arc deposition, sol-gel, sputtering, CVD, etc.). The layer is required to be sufficiently electrically conductive to enable viable electrical output while being chemically inert toward components of the photoelectrochemical cell.
- Considering conductive properties of such layers, the invention also provides for these layers being formed directly on substrate (glass, polymeric materials) without an intermediate metallic component, when requirement for electrical conductance are not high (e.g., —for low light conditions or small cell size).
- This invention is based on realisation that some materials such as titanium nitride form pinhole free strongly bound coatings that protect metallic conductors and, at the same time, provide electrical conductivity sufficient for successful operation of PEC device. Our experiments demonstrated that although unprotected 316 stainless steel substrate corrodes within several days of operation at room temperature, causing irreversible damage to electrolyte of the PEC device, a thin and dense layer of TiN coating deposited on the same substrate ensures many months of successful operations at 75° C.
- Further analysis demonstrated that certain non-metallic materials satisfy requirements of corrosion protection and electrical conductivity by way of a several micron thick film.
- These include: diamond and semimetallic, metallic (and multimetal) nitrides, carbides, oxides, borides, phosphides, silicides, antimon ides, arsen ides, tellurides and combinations thereof (e.g oxynitrides, arsenide sulphides).
- Still preferred materials for the purpose of this invention are: titanium nitride (TiN), zirconium nitride and boron carbide.
- Further preferred materials include silicides of niobium, molybdenum, tantalum, tungsten or vanadium.
- While this invention provides for a range of certain materials to be used for protection of the said metallic conductors, further description uses TiN as an example.
- In accordance with one aspect of the invention a TiN layer is deposited on metal foil or plate (e.g., stainless steel foil), thus protecting the foil from electrolyte of the cell.
- The foil or plate serves as a substrate for either working or counter electrode of the photoelectrochemical cell.
- In accordance with another aspect of the invention a TiN layer is deposited on metallic mesh, used to conduct electrical current generated locally inside a cell to the external terminals. The mesh could be used in either or both working or/and counter electrodes of a photoelectrochemical cell.
- In accordance with a further aspect of the invention, a TiN layer is deposited on metallic conductor used to interconnect photoelectrochemical cells in a series connected module. In this case both the working electrode and the counter electrode are divided each into electrically isolated portions, and the said metallic conductor connects at least one portion of the working electrode to a portion of the counter electrode
- Having broadly portrayed the nature of the present invention, embodiments thereof will now be described by way of example and illustration only. In the following description, reference will be made to the accompanying drawings in which:
-
FIG. 1 is an enlarged cross sectional view of a PEC device formed in accordance with one example of the invention. -
FIG. 2A is an enlarged cross sectional of a PEC device formed in accordance with another example of the invention. -
FIG. 2B is a diagrammatic view of a stainless steel mesh protected by a TiN coating. -
FIG. 3 is an enlarged cross sectional of a PEC device formed in accordance with further example of the invention. - Referring to
FIG. 1 the working electrode substrate comprisesStainless Steel foil 1 protected byTiN coating 2. Working electrode 3 (dye sensitised TiO2) formed on TiN coating (3 microns thick, filtered plasma deposition). The counter electrode 5 (thin dispersed Pt catalytic layer) of the device is formed on transparent electrically conductive substrate 6 (polymeric film coated by TEC). -
Electrolyte 4 is placed between the two electrodes. The device is sealed by silicone basedsealant 7. This device is to be illuminated from the counter electrode side. - Referring to
FIG. 2A , astainless steel foil 1 protected byTiN coating 2 supports counterelectrode 5 of a PEC device. The working electrode is supported by a transparent electricallyconductive substrate 6, to which astainless steel mesh 8 coated byTiN 2 is attached. The said stainless steel mesh enhances electrical connection to a working electrode 3 (dye sensitised TiO2). The device is sealed by silicone basedsealant 7. This device is to be illuminated from the working electrode side. - Referring to
FIG. 2B , the stainless steel mesh 8 (50m aperture, 30 m wire) is protected by aTiN coating 2. - Referring to
FIG. 3 , a PEC device is formed between twotransparent substrates 6. Each substrate is coated by a transparent electronic conductor 9 (TEC, F-doped tin oxide).Isolation lines 10 in TEC created with aid of laser radiation divide each electrode into small portions. The working electrode substrate is coated by dye sensitised TiO2 layer 3 and counter electrode substrate—by acatalytic layer electrolyte 4. A conductor is used to connect the cells in series. The conductor comprisesstainless steel core 11 protected by aTiN coating 12.
Claims (11)
Applications Claiming Priority (1)
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PCT/AU2004/000590 WO2004100196A1 (en) | 2003-05-05 | 2004-05-05 | Photoelectrochemical device |
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US10/555,867 Abandoned US20060243587A1 (en) | 2004-05-05 | 2004-05-05 | Photoelectrochemical device |
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Cited By (17)
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US20100071743A1 (en) * | 2006-07-06 | 2010-03-25 | Ryohsuke Yamanaka | Dye-sensitized solar cell module and method of producing the same |
WO2010043208A1 (en) * | 2008-10-15 | 2010-04-22 | H2 Solar Gmbh | Silicides for photoelectrochemical water splitting and/or the production of electricity |
US20110114503A1 (en) * | 2010-07-29 | 2011-05-19 | Liquid Light, Inc. | ELECTROCHEMICAL PRODUCTION OF UREA FROM NOx AND CARBON DIOXIDE |
WO2011112620A2 (en) * | 2010-03-08 | 2011-09-15 | University Of Washington | Composite photoanodes |
US20110226632A1 (en) * | 2010-03-19 | 2011-09-22 | Emily Barton Cole | Heterocycle catalyzed electrochemical process |
US20110226325A1 (en) * | 2010-03-17 | 2011-09-22 | Sony Corporation | Photoelectric conversion device |
US8313634B2 (en) | 2009-01-29 | 2012-11-20 | Princeton University | Conversion of carbon dioxide to organic products |
WO2013035118A1 (en) | 2011-09-08 | 2013-03-14 | Dyepower | Process of manufacturing of the catalytic layer of the counter-electrodes of dye-sensitized solar cells |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US8562811B2 (en) | 2011-03-09 | 2013-10-22 | Liquid Light, Inc. | Process for making formic acid |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US8592633B2 (en) | 2010-07-29 | 2013-11-26 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
US8658016B2 (en) | 2011-07-06 | 2014-02-25 | Liquid Light, Inc. | Carbon dioxide capture and conversion to organic products |
US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
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US10119196B2 (en) | 2010-03-19 | 2018-11-06 | Avantium Knowledge Centre B.V. | Electrochemical production of synthesis gas from carbon dioxide |
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US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8592633B2 (en) | 2010-07-29 | 2013-11-26 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
US20110114503A1 (en) * | 2010-07-29 | 2011-05-19 | Liquid Light, Inc. | ELECTROCHEMICAL PRODUCTION OF UREA FROM NOx AND CARBON DIOXIDE |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US9309599B2 (en) | 2010-11-30 | 2016-04-12 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
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