+

WO1999063599A1 - Cellule photovoltaique a aspect tandem, nanostructuree et sensible au colorant - Google Patents

Cellule photovoltaique a aspect tandem, nanostructuree et sensible au colorant Download PDF

Info

Publication number
WO1999063599A1
WO1999063599A1 PCT/SE1999/000290 SE9900290W WO9963599A1 WO 1999063599 A1 WO1999063599 A1 WO 1999063599A1 SE 9900290 W SE9900290 W SE 9900290W WO 9963599 A1 WO9963599 A1 WO 9963599A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
dye
photo
working electrode
nano
Prior art date
Application number
PCT/SE1999/000290
Other languages
English (en)
Inventor
Sten-Eric Lindquist
Anders Hagfeldt
Original Assignee
Lindquist Sten Eric
Anders Hagfeldt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lindquist Sten Eric, Anders Hagfeldt filed Critical Lindquist Sten Eric
Priority to AU32841/99A priority Critical patent/AU3284199A/en
Publication of WO1999063599A1 publication Critical patent/WO1999063599A1/fr

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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
    • H01G9/2072—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells comprising two or more photoelectrodes sensible to different parts of the solar spectrum, e.g. tandem cells
    • 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

Definitions

  • the present invention relates to a photo-voltaic cell, in particular one having a cell structure comprising two electrodes with an electrolyte located there between, and where at least one of the electrodes has an active surface in the form of a dye sensitized nano-structured film.
  • Photo-voltaic cell commonly referred to as solar cells
  • solar cells have a potential of having a breakthrough on the energy market for the generation of electricity directly from the sun light.
  • the critical factor will be the cost at which the energy generated by the sun can be produced.
  • the solar cell technology has been developed and the cost per kWh has been reduced.
  • Solar cells at prices accepted by the market for the production of electricity are today available only in special fields of use. For a more general utilization of electrical power produced by solar cells, cheaper and more efficient solar cells are required.
  • the traditional solar cells are based on either a Schottky-barrier between a metal and a semiconductor, or on a so called p-n junction in one and the same semi-conductor material.
  • a photo-voltage and a current is generated on illumination of the Schottky-barrier or the p-n junction alternatively.
  • the early variants of such cells were based on crystalline materials. High purity was necessary in order to achieve a high efficiency. However, crystalline systems become expensive and they can today for economic reasons not be employed in large scale generation of electrical power.
  • To overcome this problem a number of different solar cells have been developed in thin film technology. The most well known and promising cells are constructed from amorphous silicon. The amorphous silicon solar cells have been possible to handle by creating cells made up of several thin layers, doped as p-i-n, where "i" stands for intrinsic (undoped) layer.
  • CdS cadmium sulfide
  • DSC Density Sensitized Solar cell
  • M. Gratzel at EPFL in Lausanne, Switzerland (see EP-A-0 333 641, WO 95/18456, US-A-5,350,644, US- A-5,525,544, US-A-5 ,441,827, alia Gratzel et al). Cells of this type are known since the late 70's, when they were studied e.g. by a number of Japanese researcher.
  • DSC differs significantly from the classical Schotty-barrier cells with junction of the p-n or p-i-n type.
  • a cell comprises a working electrode, an electrolyte and a counter electrode.
  • the working electrode is sensitized with a dye, to render it photo-active in the visible spectrum (sun light).
  • This dye sensitized, nano-porous, nano-crystalline (or nano-structured) thin film solar cell presented by O'Reagan and Gratzel in Nature 1991, thus has a photo-active anode and a passive cathode, only serving to in an efficient way regenerate the redox-species that is oxidized at the sensitized, nano-structured photo anode.
  • This type of cell usually reaches cell efficiencies of 6-9%, although 11% has been reported.
  • the upper theoretical limit is about 30%.
  • a possibility to increase the efficiency would be to combine the Gratzel/O' Reagan cell with a photo-active cathode of a p-type poly-crystalline or single-crystalline semi-conductor, with a low band-gap.
  • Example thereof could be p-CdSe, p-CdTe, p-InP etc.
  • these semiconductors are unstable in most electrolytes.
  • a photo-voltage may be registered at the terminal connections of the cell, and if the circuit is closed with an external lead, an electrical work can be performed externally of the cell.
  • the maximum value of the photo-voltage, Uoc is the difference between the energy level of the redox couple in the solution, and the level of the conduction band.
  • the photo- current will be directly dependent on the number of absorbed photons, resulting in the injection of electrons in the conduction band, and on any losses of electrons back to the electrolyte, which take place during the transport thereof towards the back contact.
  • the primary drawback with prior art solar cells, briefly described above, is in practice their low _ efficiency.
  • the object of the invention is to provide a thin film solar cell having a higher photo voltage, and thereby a higher efficiency. This is achieved by a dye sensitized solar cell of the tandem type, wherein both the anode and the cathode are photo-active and wherein at least one electrode, preferably both, are dye sensitized.
  • the invention is defined in claim 1.
  • the valence band of the photo-active cathode is at an energy level which is above the HOMO level (Highest Occupied Molecular Orbital) for the dye with which the cathode has been sensitized.
  • the conduction band of the anode lies at a level which is below the LUMO level (Lowest Occupied Molecular Orbital) for the dye with which the anode has been sensitized.
  • the HOMO level of the dye for the anode is lower than the level of the redox- couple, and the LUMO level of the cathode is higher than the level of the redox-couple.
  • the cell structure according to the present invention thereby forms a tandem cell, in that the counter electrode also constitutes a photo-active electrode, whereby the photo-active working electrode and/or the photo-active electrode is made up on a transparent substrate. Also, both the photo-active working electrode and the photo-active electrode comprise porous, nano- structured film.
  • the photo-active electrodes are dye sensitized with a first and a second dye, respectively.
  • the first dye is selected such that the electron injection into the working electrode is so fast, that the red-form of a redox-couple in the electrolyte, as fast as possible replaces an injected electron.
  • the other dye is selected to have a long lived excited state.
  • the material in the counter electrode is a semi-conductor having a large band-gap.
  • the working electrode is dye sensitized, corresponding to the first embodiment, whereas the counter electrode comprises a semi-conductor having a band-gap absorbing in the visible and/or infrared range, whereby the light absorption in this electrode is further enhanced by a dye, absorbed onto the surface of said electrode.
  • Figure 1 shows a cross section through a prior art sandwich cell of the DSC type
  • Figure 2a shows a cross section through a DSC, which also shows, on a vertical scale, the energetic relations between semi-conductor, dye and electrolyte,
  • Figure 2b shows schematically the spectral light absorption for the dye and the semi- conductor material in the prior art DSC type
  • Figure 3 shows a cross section through a prototype of a sandwich cell of the TDSC type in accordance with the invention
  • Figure 4a shows another cross section through TDSC according to the invention, showing on the vertical scale the energetic relations between semi-conductor, dye and electrolyte,
  • Figure 4b shows schematically the spectral light absorption in the first and second dye respectively, and in the semi-conductor materials for the embodiment disclosed in Figure 4a,
  • FIG. 5a shows cross section through a further embodiment a TDSC in accordance with the invention
  • Figure 5b shows schematically the spectral light absorption in the first and second dye respectively, and in the semi-conductor materials for the embodiment disclosed in Figure 5 a,
  • Figure 6 shows iV characteristics for a dye sensitized NiO electrode in three electrode set-up vs Ag/AgCl electrode
  • Figure 7a shows iV characteristics of a dye sensitized TiO 2 electrode
  • Figure 7b shows iV characteristics of a dye sensitized NiO electrode
  • Figure 7c shows iV characteristics of a tandem cell comprising a dye sensitized TiO 2 electrode and a dye sensitized NiO electrode.
  • FIG. 1 shows schematically the design of a DSC.
  • the working electrode e.g. comprises transparent carrier substrate Imade of glass or plastics, having a transparent thin film back contact 2, made e.g. of SnO 2 (F).
  • the thin film (of the order 1-10 ⁇ m) comprises sintered oxide particles 3 covered by a mono-layer of a dye 4.
  • the electrolyte 5 comprises a redox-system with suitable redox-couples.
  • the counter electrode CE comprises a catalytic layer 8 on a transparent or opaque conducting film 9 on glass 10 or on an opaque conducting substrate.
  • the most efficient redox-system used today is the iodine/iodide system.
  • the redox-system performs the charge transport between the two electrodes.
  • One of the electrodes, which is a passive electrode, is here referred to as the counter electrode CE.
  • the active electrode WE is constructed of a film, typically 5-10 ⁇ m thick, of a so called nano-structured material, i.e. a porous material of particles having dimensions in the nanometer range.
  • the particles are sintered together to a solid film (if the material is comprised of nano-rods the rods may preferably be oriented perpendicularly against the underlying film, with the same dimension as the film thickness). It is essential that the cross section at right angles to the film will have a very large internal surface.
  • the film is located on a conducting transparent substrate, e.g. of SnO 2 (f), ITO or the like, which in its turn is located on a transparent carrier material, e.g. glass or plastics.
  • a metal mesh can be place under, in or on the conducting transparent film.
  • the nano-structure in the active film can be comprised of a semi-conductor or an insulator, e.g. an oxide having a large band-gap. A common oxide in this connection is TiO 2 .
  • the oxide particles (or rods) are sintered together to a porous matrix.
  • the porosity is typically about 50%, which means that the electrolyte can penetrate the thin film all the way up to the conducting back contact. If the above mentioned oxide films are used, they will normally have their absorption in the UV range and cannot by themselves _ catch any larger portion of the sun light. However, if the surface of the particles (rods) are dyed with a dye having its absorption in the visible part of the solar spectrum, the efficiency can be improved substantially. A DSC is obtained. DSC prototypes having efficiencies of up to 1% have been made in this way (see Gratzel). The reason that the cell works is i.a. that the inner surface of the nano-structured thin film on the active electrode is very large, typically 1000 times larger than the geometrically illuminated surface.
  • Figure 2a shows in an energy diagram how the dye sensitized cell works energetically
  • figure 2b shows schematically the spectral light absorption of the dye and the semi-conductor material SCI, respectively, in the described prior art DSC.
  • the left hand vertical axis corresponds to energy (E/eV), which can also be expressed as a potential (V) according to the right hand axis.
  • SCI indicates the nano-structured porous semi-conductor oxide, with the levels of the valence band VB and the conduction band CB inserted. Furthermore, the energy level of the dye Dye 1 is inserted.
  • the conduction band CB of the semi-conductor film is below the lowest unoccupied electronic energy level, LUMO, of the dye. Also, it is important that the energy level Ured/ox of the redox-couple energetically is above the highest occupied electron energy level HOMO. This is required in order to obtain a driving force for the electron transitions.
  • a complete cycle for the motion of an electron through the cell will be as follows: upon photon excitation electrons will be lifted from the HOMO level of the dye to its LUMO level.
  • the electrons in the LUMO level of the dye are injected into the conduction band of the oxide film, an extremely fast process with a half life of less than 100 femtoseconds. Therefrom they can pass out through the back contact and through an external lead transferred to the CE. This can be a relatively slow process with transit times in the millisecond range.
  • At the CE they are received by the oxidized form (Ox) of the redox-couple which is in the electrolyte. Thereby the Ox is reduced and the red-form (Red) is obtained.
  • Ox oxidized form
  • Figures 3-5 illustrate the principle of a dye sensitized tandem cell TDSC in accordance with the present invention.
  • Figure 3 shows a cross section through a basic prototype of a sandwich cell of the TDSC type. In such a TDSC at least one electrode WEI or WE2 is built on a transparent substrate having a conducting transparent film. The figure shows a TDSC where both electrodes have transparent substrates with a conducting transparent film.
  • the counter electrode in the simple dye sensitized cell has been replaced by a photo-active electrode, WE2.
  • WEI as well as WE2 thus are photo-active. This contributes to increase the cell efficiency.
  • At least one of the electrodes is dye sensitized and built up of a porous, nano-structured film. This electrode will be designated WEI below.
  • WEI The function of WEI is identical to what has been disclosed above for WE of Figure 1. It is dye sensitized by a first dye.
  • at least one electrode, WEI or WE2 are built on a transparent substrate having a conducting transparent film. If one of the electrodes is built on a transparent substrate with a conducting transparent film, sun light will impinge first on this electrode.
  • Figure 4a there is shown a cross section through a TDSC in accordance with the invention.
  • Figure 4a shows on its vertical scale the energetic relations between semi-conductor, dye and electrolyte, all at the same time.
  • E/eV energy scale
  • V/Volts potential scale
  • SCI is the nano-structured porous semi-conductor oxide, with the levels of the valence band VB and the conduction band CB inserted.
  • the energy levels of the first dye, Dye 1 are inserted whereby HOMO 1 represents the lower level and LUMO 1 represents the higher level.
  • Ered/Ox indicates the energy level of the redox-system.
  • SC2 is a nano-structured porous semi-conductor oxide with a large band-gap, and with the levels of the valence band VE and of the conduction band CB inserted.
  • the energy levels for the second dye, Dye2 are inserted in a way corresponding to the first dye, whereby HOMO2 represents the lower level and LUMO2 represents the higher level.
  • the electron transport after photo-excitation with photon energies hvj and hv 2 are indicated with electrons 'e', and by direction arrows placed adjacent 'e'.
  • FIG. 5a shows a corresponding cross section through a TDSC.
  • Fgiure 5a is essentially the same as Figure 4a, but with an altered working electrode WE2.
  • SC2 constitutes a nano-structured porous semi-conductor oxide with a long band-gap, and with the levels of the valence band VB and the conduction band CB inserted.
  • the electron transport after photo- excitation with photon energies hvi and hv are indicated with electrons 'e', and by direction arrows placed adjacent 'e'.
  • the second dye and SC2 cooperate for increased photo current in WE2.
  • Figure 5b shows schematically, corresponding to figure 4b, the spectral light absorption in the first dye, Dyel, and in the second dye, Dye2, as well as in the semi-conductor materials SCI and SC2, in this other embodiment of the TDSC according to the invention.
  • SC2 now has its absorption in the visible and/or infra red range.
  • both WEI and WE2 are comprised of porous nano-structured films, two variants can be distinguished (See I and II below).
  • the porous film can be grown directly outwards from the underlying conducting substrate. This could have manufacturing technological advantages, since the film can be made at a low temperature. Cheap substrates of plastics will then become possible to use.
  • the material in the particles in WE2 are comprised of a semi-conductor having a large band-gap (3 eV or higher), e.g. zink selenide (ZnSe), silicon carbide (SiC) or some other semi-conductor with a high band-gap, which in order to become photo-active must be dye sensitized.
  • a semi-conductor having a large band-gap 3 eV or higher
  • ZnSe zink selenide
  • SiC silicon carbide
  • the material in the particles in WE2 are comprised of a semi-conductor having a band-gap which in itself has an efficient absorption in the visible and/or infra red spectral range.
  • the principle is illustrated in Figures 5a and 5b, and the function of the two variants are describe in detail below.
  • WE2 is a porous nano-structured semi-conductor with a large band-gap, the intrinsic absorption of which is in the UV -range, WE2 must be dye sensitized in order that the light absorption of the electrode also take place in the visible and/or infra red range. Further, it is - necessary that the energy levels of the second dye is correctly tuned against the energy levels in WE2, such that the HOMO level of the second dye is below VB of the semi-conductor material in WE2. Semi-conductor material in WE2 can advantageously be p-doped. The other energy levels of the dye sensitized electrodes WEI and WE2 must be tuned against the redox- couple that is active in the electrolyte.
  • the energy level of the redox-couple must be below the LUMO level of the second dye, and above the HOMO level of the first dye.
  • the principle for this type of cell in energetic terms is given in figure 4a.
  • a schematic drawing of the spectral distribution of the absorption in a solar cell is given in Figure 4b.
  • the first dye is selected such that the electron injection into the electrode material WEI is so fast as possible, and such that the red-form (Red) of the redox-couple will replace the injected electron as fast as possible.
  • WE2 is characterized in that the second dye should have a long lived excited state, i.e. the electron should live long in the sLUMO level of the second dye molecule. This is achieved most easily if the second dye has a long lived triplet state, into which a singlet state will be quantitatively transformed after the photon energy has been absorbed in the second dye. Long life of the excited state is necessary in order that the second dye molecule will have time enough to donate its electron to the oxo form (Ox) of the redox-couple.
  • Ox oxo form
  • a photon is absorbed in the first dye, whereby an electron is raised in energy from the first HOMO 1 level to the first LUMO 1 level
  • the electron in SC 1 reaches the back contact and passes through the external lead via an ohmic back contact to the VB of the nano-structured SC2 material
  • a photon is absorbed in the first dye, whereby an electron is raised in energy from the second HOMO level to the second LUMO2 level
  • the electron in the second LUMO2 reduces Ox to Red
  • An electron is transferred from the VB of SC2 to the HOMO2 level of the second dye
  • WE2 is a semi-conductor with a band-gap having its absorption in the visible and/or infra red region, it can constitute a photo-active electrode, if its absorption spectrum and absorption is correctly tuned against the dye sensitized electrode WEI, and its other energy levels are tuned against the active redox-couple in the electrolyte, and the energy levels in WEI, although it is not dye sensitized.
  • the material in the particles would then be comprised of some (intrinsic or p-doped) semi-conductor, e.g.
  • WEI dye sensitized
  • WE2 is a semiconductor having a band-gap with absorption in the visible and/or infra red range.
  • WEI is the dye sensitized electrode
  • WEI is a semi-conductor having a band-gap in the visible and/or infra red range.
  • a larger or smaller amount of dye can be adsorbed in a mono-layer to the inner surface of the electrode material, and in this way it is possible to tune WE2 against WEI such that the desired balance between the number of absorbed photons in the two photo-electrodes is obtained.
  • the maximum value of the photo voltage Uoc TDSC is the difference between the energy levels VB in WE2 and CB in WEI . One can thus expect a substantially higher photo voltage from a TDSC device compared to a prior art DSC device.
  • a TDSC cell has a WEI electrode which is an electrode made of porous titanium dioxide (TiO 2 ), dyed with a ruthenium dye, comprised of a ruthenium bis-pyridine complex of a known type.
  • a large number of dyes are conceivable.
  • a very thin layer of a semi-conductor can be used. Such a semi-conductor is of course assumed to absorb in the visible and infra red part of the light spectrum. Functional groups binding to the titanium dioxide surface (e.g.
  • the electrode WE2 is comprised of porous, nano-structured, p-doped silicon carbide (SiC), which has been dye sensitized with a dye (B) Ru(bpy)(Bpz) , wherein bpy is bipyridine ligand and bpz is a bi(l,4)diazine ligand rutenium complex [Inorg. Chem. 22, (1983), 224], the HOMO level of which is below the valence band of the silicon carbide.
  • I 2 /T iodine/iodide system
  • solvent acetonitril or some other correspondingly polar solvent e.g. an iodine/iodide system (I 2 /T) is used in the solvent acetonitril or some other correspondingly polar solvent.
  • the total content of I 2 is typically 50 mM and the total content off is typically 1,0 M.
  • the cell in this example is in all details as in the embodiment 1 , but with the difference that the silicon carbide SiC has been replaced by nano-particles of Fe 2 O 3 .
  • the cell in this example is in all details as in the embodiment 3, but with the addition that nano-crystalline rods of Fe O 3 in the ⁇ m size constitute the active porous nano-structure in WE2.
  • the cell in this example is in all details as in the embodiment 4, with the addition the nano- crystalline rods of Fe 2 O 3 are anisotropically arranged with an orientation at right angles to the plane of the substrate.
  • the cell in this example is in all details as in the embodiments 3, 4 and 5, but the inner surface of the Fe 2 O 3 film is provided with a mono-layer of dye sensitizing substance.
  • An electrode having a "p-type behavior" was made from a transparent substrate in the form of a glass plate having an electrically conducting coating, on which had been deposited nano- structured NiO.
  • the average diameter of the particles were 10-20 nm. They were applied onto the glass substrate with a doctor blade technique, which is type of gel coat technique.
  • a spacer (a few tens ⁇ m thick) was glued in parallel along two edges of the conducting glass. A viscous solution containing the colloidal nano-particles was added. Excess solution was raked off. When the film had dried the spacer strips were removed and the film was sintered at about 500°C.
  • NiO is known as a semi-conductor with a large band-gap (3,6 - 4,0 eV) and has a tendency to exhibit "p-type behavior" as prepared.
  • EXAMPLE 8 is known as a semi-conductor with a large band-gap (3,6 - 4,0 eV) and has a tendency to exhibit "p-type behavior" as prepared.
  • the electrode from Example 6 was dye sensitized by coating it with tetrakis(4-carboxy- phenyl)porphyrin (TPPC). Also this electrode (in the same electrolyte) exhibits p-type behavior on illumination with 1000W solar simulator (lamp: Xenon). This is illustrated in Figure 6.
  • TPPC tetrakis(4-carboxy- phenyl)porphyrin
  • the electrode from Example 8 was mounted as photo electrodes in a measurement set-up with a Pt electrode as a counter electrode.
  • Figure 6b shows the iV characteristics for this nano-structured NiO electrode.
  • the photo voltage is about 110 mV.
  • the electrodes tested separately in Example 9, are mounted in a tandem cell such that the NiO electrode functions as the cathode, and the TiO 2 electrode as the anode.
  • Photo voltages of at least 1,5 V, preferably about 2,0 V are fully achievable using this principle.
  • Other dyes are also conceivable, e.g. Erythrosin B.
  • Further variations of the embodiments can be achieved by the skilled man by employing prior art teachings. Since each component in each individual electrode WEI and WE2, as well as the components in the electrolyte can be varied, the number of possible embodiments is large.
  • TiO 2 in WEI ZnO could e.g. be used.
  • ruthenium polypyridine complexes other dye categories could be used, e.g. porphyrins and phtalocyanines.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un dispositif permettant d'obtenir une structure cellule photovoltaïque, nanostructurée et sensibilisée au colorant, d'efficacité accrue. Cette cellule comprend une électrode de référence photo-active (WE1), une contre-électrode (WE2) et un électrolyte (5) intermédiaire. Cette structure cellule est constituée d'une cellule à aspect tandem en ce sens que la contre-électrode est également une électrode photo-active, l'électrode de référence photo-active et/ou l'électrode photo-active étant montées sur un substrat transparent. En outre, l'électrode de référence photo-active tout comme l'électrode photo-active sont réalisées dans un film nanostructuré poreux et l'électrode de référence photo-active est sensibilisée à un premier colorant (Colorant 1) qui est sélectionné de telle façon que l'injection d'électrons dans l'électrode de référence soit rapide de telle façon que la forme rouge du couple rédox dans l'électrolyte remplace le plus vite possible un électron injecté. Le deuxième colorant (Colorant 2) est sélectionné de telle façon qu'il ait un état d'excitation de longue durée. Dans ce cas, la matière de la contre-électrode est constituée d'un semi-conducteur d'une grande largeur de bande. En variante, l'électrode de référence est sensibilisée au colorant correspondant au premier mode de réalisation. La contre-électrode étant constituée d'un semi-conducteur d'une largeur de bande dont l'absorption se situe dans le visible et/ou la plage infra-rouge. L'absorption de la lumière dans l'électrode est en outre améliorée par un colorant absorbé à la surface de cette électrode.
PCT/SE1999/000290 1998-05-20 1999-03-01 Cellule photovoltaique a aspect tandem, nanostructuree et sensible au colorant WO1999063599A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32841/99A AU3284199A (en) 1998-05-20 1999-03-01 Dye sensitized nano-structured photo-voltaic tandem cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9801799-9 1998-05-20
SE9801799A SE9801799D0 (sv) 1998-05-20 1998-05-20 Färgämnessensiterad nanostrukturerad fotovoltaisk tandemcell

Publications (1)

Publication Number Publication Date
WO1999063599A1 true WO1999063599A1 (fr) 1999-12-09

Family

ID=20411404

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1999/000290 WO1999063599A1 (fr) 1998-05-20 1999-03-01 Cellule photovoltaique a aspect tandem, nanostructuree et sensible au colorant

Country Status (3)

Country Link
AU (1) AU3284199A (fr)
SE (1) SE9801799D0 (fr)
WO (1) WO1999063599A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6783868B2 (en) 2001-04-02 2004-08-31 Air Products And Chemicals, Inc. Halogen addition for improved adhesion of CVD copper to barrier
EP1513171A1 (fr) * 2003-09-05 2005-03-09 Sony International (Europe) GmbH Cellule solaire sensibilisé par un colorant et méthode pour sa fabrication
EP1562205A1 (fr) * 2004-02-03 2005-08-10 Samsung SDI Co., Ltd. Cellules solaires sensibilisées par un colorant et leur procédé de fabrication
WO2005104153A1 (fr) * 2004-04-23 2005-11-03 Sony Deutschland Gmbh Procede de production d'un film semi-conducteur poreux sur un substrat
WO2005124802A1 (fr) * 2004-06-15 2005-12-29 Dyesol Ltd Dispositifs photovoltaiques et dispositifs mixtes de production et de stockage d'energie utilisant 100 % de la surface efficace
US7012842B2 (en) 2002-06-28 2006-03-14 Progressant Technologies, Inc. Enhanced read and write methods for negative differential resistance (NDR) based memory device
EP1673790A1 (fr) * 2003-05-21 2006-06-28 Sustainable Technologies International PTY Ltd Combinaison d'une cellule photoelectrochimique et d'un condensateur
JP2009016158A (ja) * 2007-07-04 2009-01-22 Konica Minolta Business Technologies Inc 光電変換素子
US8237046B2 (en) * 2004-01-20 2012-08-07 Sharp Kabushiki Kaisha Dye-sensitized solar cell module
US10954567B2 (en) 2012-07-24 2021-03-23 Pharmacyclics Llc Mutations associated with resistance to inhibitors of Bruton's Tyrosine Kinase (BTK)
US11189432B2 (en) 2016-10-24 2021-11-30 Indian Institute Of Technology, Guwahati Microfluidic electrical energy harvester

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416959A (en) * 1980-11-18 1983-11-22 Terje Skotheim Photoelectrochemical cells for conversion of solar energy to electricity
US5084365A (en) * 1988-02-12 1992-01-28 Michael Gratzel Photo-electrochemical cell and process of making same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416959A (en) * 1980-11-18 1983-11-22 Terje Skotheim Photoelectrochemical cells for conversion of solar energy to electricity
US5084365A (en) * 1988-02-12 1992-01-28 Michael Gratzel Photo-electrochemical cell and process of making same

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6783868B2 (en) 2001-04-02 2004-08-31 Air Products And Chemicals, Inc. Halogen addition for improved adhesion of CVD copper to barrier
US7012842B2 (en) 2002-06-28 2006-03-14 Progressant Technologies, Inc. Enhanced read and write methods for negative differential resistance (NDR) based memory device
EP1673790A4 (fr) * 2003-05-21 2011-09-28 Dyesol Ind Pty Ltd Combinaison d'une cellule photoelectrochimique et d'un condensateur
EP1673790A1 (fr) * 2003-05-21 2006-06-28 Sustainable Technologies International PTY Ltd Combinaison d'une cellule photoelectrochimique et d'un condensateur
AU2004271247B2 (en) * 2003-09-05 2009-08-27 Sony Deutschland Gmbh Tandem dye-sensitised solar cell and method of its production
EP1513171A1 (fr) * 2003-09-05 2005-03-09 Sony International (Europe) GmbH Cellule solaire sensibilisé par un colorant et méthode pour sa fabrication
WO2005024866A1 (fr) * 2003-09-05 2005-03-17 Sony Deutschland Gmbh Cellule solaire en tamdem photosensible au colorant et son procede de production
US8237046B2 (en) * 2004-01-20 2012-08-07 Sharp Kabushiki Kaisha Dye-sensitized solar cell module
EP1562205A1 (fr) * 2004-02-03 2005-08-10 Samsung SDI Co., Ltd. Cellules solaires sensibilisées par un colorant et leur procédé de fabrication
US7935263B2 (en) 2004-04-23 2011-05-03 Sony Deutschland Gmbh Method of producing a porous semiconductor film on a substrate
WO2005104153A1 (fr) * 2004-04-23 2005-11-03 Sony Deutschland Gmbh Procede de production d'un film semi-conducteur poreux sur un substrat
US8319098B2 (en) 2004-04-23 2012-11-27 Sony Deutschland Gmbh Porous semiconductor film on a substrate
US7649140B2 (en) 2004-06-15 2010-01-19 Dyesol Ltd. Photovoltaic module with full utilization of surface area
AU2005255501B2 (en) * 2004-06-15 2009-01-08 Dyesol Ltd Photovoltaic module with full utilization of surface area
WO2005124802A1 (fr) * 2004-06-15 2005-12-29 Dyesol Ltd Dispositifs photovoltaiques et dispositifs mixtes de production et de stockage d'energie utilisant 100 % de la surface efficace
JP2009016158A (ja) * 2007-07-04 2009-01-22 Konica Minolta Business Technologies Inc 光電変換素子
US10954567B2 (en) 2012-07-24 2021-03-23 Pharmacyclics Llc Mutations associated with resistance to inhibitors of Bruton's Tyrosine Kinase (BTK)
US11189432B2 (en) 2016-10-24 2021-11-30 Indian Institute Of Technology, Guwahati Microfluidic electrical energy harvester

Also Published As

Publication number Publication date
SE9801799D0 (sv) 1998-05-20
AU3284199A (en) 1999-12-20

Similar Documents

Publication Publication Date Title
Grätzel Dye-sensitized solar cells
Janne Dye-sensitized nanostructured and organic photovoltaic cells: technical review and preliminary tests
Grätzel et al. Artificial photosynthesis: efficient dye-sensitized photoelectrochemical cells for direct conversion of visible light to electricity
US7087834B2 (en) Apparatus and method for photovoltaic energy production based on internal charge emission in a solid-state heterostructure
Grätzel The artificial leaf, molecular photovoltaics achieve efficient generation of electricity from sunlight
Grätzel Mesoporous oxide junctions and nanostructured solar cells
Grätzel Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells
Francis et al. Review of dye-sensitized solar cell (DSSCs) development
EP2224534B1 (fr) Module de cellule solaire photosensibilisée et son procédé de fabrication
Lenzmann et al. Recent advances in dye‐sensitized solar cells
Wang et al. Boosting the photocurrent density of p-type solar cells based on organometal halide perovskite-sensitized mesoporous NiO photocathodes
Xiong et al. Recent progress on tandem structured dye-sensitized solar cells
Nwanya et al. Dyed sensitized solar cells: A technically and economically alternative concept to pn junction photovoltaic devices.
WO1999063599A1 (fr) Cellule photovoltaique a aspect tandem, nanostructuree et sensible au colorant
Ishii et al. A high voltage organic–inorganic hybrid photovoltaic cell sensitized with metal–ligand interfacial complexes
Leite Nanostructured materials for electrochemical energy production and storage
Grätzel Nanocrystalline electronic junctions
Grätzel Nanocrystalline thin-film PV cells
Mahesh et al. TiO2 microstructure, fabrication of thin film solar cells and introduction to dye sensitized solar cells
Bai et al. Advancements in the development of various types of dye-sensitized solar cells: a comparative review
Grätzel Nanocrystalline ceramic films for efficient conversion of light into electricity: Code: F9
Son et al. Effect of ultraviolet radiation on the long-term stability of dye-sensitized solar cells
WO2004025748A1 (fr) Dispositif photovoltaique comprenant un compose 1,3,5-tris-aminophenyl-benzene
JP4094319B2 (ja) 薄膜層を有する複合半導体
Grätzel Properties and applications of nanocrystalline electronic junctions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

WWE Wipo information: entry into national phase

Ref document number: 09700760

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载