WO2001011702A1 - Electrode et cellule photoelectrochimique a quatre couches, procede de production d'une pate pouvant etre imprimee, contenant un electrolyte et/ou du carbone, et d'une electrode - Google Patents

Electrode et cellule photoelectrochimique a quatre couches, procede de production d'une pate pouvant etre imprimee, contenant un electrolyte et/ou du carbone, et d'une electrode Download PDF

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Publication number
WO2001011702A1
WO2001011702A1 PCT/DE2000/002723 DE0002723W WO0111702A1 WO 2001011702 A1 WO2001011702 A1 WO 2001011702A1 DE 0002723 W DE0002723 W DE 0002723W WO 0111702 A1 WO0111702 A1 WO 0111702A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
electrode
layer
paste
photoelectrochemical cell
Prior art date
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Ceased
Application number
PCT/DE2000/002723
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German (de)
English (en)
Inventor
Georg Mermigidis
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Individual
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Individual
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Priority to EP00965749A priority Critical patent/EP1125335A1/fr
Publication of WO2001011702A1 publication Critical patent/WO2001011702A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a method for producing an electrolyte- or or carbon-containing, printable paste, in particular as an electrode material for a photoelectrochemical cell, a method for producing an electrode, in particular an electrolyte-containing counter electrode of a photoelectrochemical cell, and to an electrolyte-containing electrode and a photoelectrochemical Cell itself.
  • Dye-sensitized photoelectrochemical cells which use a material with a very large band gap, such as titanium dioxide, as a semiconductor. Since such a semiconductor with a large band gap leads to the fact that, in particular, low-energy solar radiation is absorbed to a lesser extent, the sensitivity in such photoelectrochemical cells is increased by a dye layer applied to the semiconductor layer.
  • the functions of light absorption and charge carrier separation which take place in a single material in conventional solar cells, such as silicon solar cells, are separated in such dye-sensitized cells. The light absorption takes place essentially in the dye-sensitized layer, also called chromophore layer, while the charge carrier separation takes place at the semiconductor / dye layer interface.
  • a ruthenium (Ru) -containing dye is preferably used as the dye for the sensitized dye layer.
  • Suitable electrolytes for such photoelectrochemical cells are iodide, bromide, hydroquinone or other redox systems.
  • Metal oxide semiconductors in particular titanium oxide, are usually used as the electrode.
  • a photoelectrochemical cell as described above is known for example from EP 0584307 B1.
  • Carbon pastes are produced, which are applied to the corresponding substrate, for example TCO glass, and then annealed or fired in order to obtain a stable layer.
  • the light-absorbing layer usually a TiO 2 layer
  • the light-absorbing layer can only be sensitized after the carbon paste has been fired or tempered, since the dye is sensitive to temperature and is destroyed during firing. As a result, a lot of dye is required for the sensitization.
  • the soot-containing paste can be produced on the basis of all suitable electrolytes that have previously been used for the photoelectrochemical cell. Basically, the soot or graphite will not have a functional interaction with the electrolytic components. The invention can thus also be used in the case of electrolytes still to be developed in the future.
  • the suspension obtained is then stirred in order to obtain an essentially homogeneous distribution. Finally, the homogenized suspension is treated with ultrasound, so that a printable, stiff paste is produced.
  • the pastes can be characterized by their impedance.
  • carbon black carbon with a high agglomeration ability and a high structure (fir tree), that is to say with a large microscopic surface and a surface-weight ratio of more than 20 m / g, here referred to as carbon black.
  • conductivity blacks those with the highest possible electrical conductivity, resistance values of maximum 10 " ⁇ are acceptable.
  • carbon with a low agglomeration ability and a small structure (wooden pile), that is to say with a small microscopic surface, but in one direction with a very low resistance, referred to here as graphite, is used.
  • the resistance of the graphite used is of the order of 10 " ⁇ or less.
  • the method according to the invention provides a printable, stiff paste which has a consistency which enables the paste to be used as an electrode or electrolyte in a photoelectrochemical cell. Burning or tempering can also be completely dispensed with. This prevents the dye from being destroyed and the light-absorbing layer can be sensitized directly with a dye layer. This avoids the high loss of dye due to the absorbing properties of carbon in carbon electrodes, so that less dye has to be used for the sensitization, which leads to a significant reduction in costs.
  • the amount of electrolyte salt can be reduced. It has been shown that a reduction to 40% of the amounts originally contained in the pure electrolyte has a favorable effect on the strength of the paste.
  • Electrolyte salts and electrolyte auxiliaries are preferably present in the solvent in a concentration such as is used for the photoelectrochemical cell, in particular for the electrolytes in a photoelectrochemical cell.
  • y-butyrolactone is used as the solvent.
  • Degussa carbon black FW 200 is particularly suitable as a carbon black with a large microscopic surface
  • Degussa carbon black XE2 is particularly suitable as a carbon black.
  • Timcal Timrex SFG 44 or Timcal Timrex SFG 75 is preferably used as graphite with a very low resistance.
  • the suspension with the added particles is preferably stirred for 5 minutes and then treated with ultrasound in an ultrasound bath for about 15 minutes.
  • the length of the ultrasound treatment depends on the radiated power and is carried out until the paste has the desired consistency.
  • the paste should have no flowability and should only be spreadable.
  • ultrasound is irradiated with a power density of approximately 1 W / cm onto a paste with a volume of 20 cm over a period of 15 minutes.
  • an electrolyte- or or carbon-containing, printable paste is provided.
  • the paste is applied to a substrate or a composite substrate and adapted.
  • the paste is applied directly to the porous light-reflecting insulator layer, which covers the light-absorbing layer which has been sensitized with a dye layer and which is arranged on an electrode of the photoelectrochemical cell.
  • the layer After the paste has been applied and pressed onto the substrate, the layer is already in its operational state; firing or annealing of the layer in order to obtain a firmer consistency is not necessary, so that a very fast and therefore inexpensive process for producing an electrolyte-containing one is necessary Electrode is provided.
  • a graphite layer is preferably also applied to the applied and pressed paste, in particular by dusting. This provides a thin, very conductive layer.
  • the graphite layer must be opaque so that there is horizontal conductivity. One or two layers of graphite particles are sufficient. The thickness of the layer is therefore dependent on the particle size of the graphite particles, but also on the sputtering technique.
  • An electrolyte-containing electrode according to the invention is used in particular as an electrolyte-containing counter electrode of a photoelectrochemical cell and comprises an electrolyte-containing, carbon-containing, printable paste.
  • This layer consisting of the electrolyte-containing, carbon-containing paste can be covered on one side with a further dusted graphite layer.
  • the electrolyte-containing electrode is preferably produced by a method as described above, the same applies to the electrolyte-, carbon-containing, printable paste.
  • the electrode can be manufactured completely at room temperature, there is no annealing or burning and subsequent lengthy filling with air bubbles Dye and electrolyte are necessary when used in a photoelectrochemical cell, so that the manufacturing process is considerably simplified and cheaper.
  • the electrolyte-containing electrode has comparable characteristics to conventional electrodes, so that no or very little power or. Loss of efficiency can be expected when using the electrolyte-containing electrode according to the invention in photoelectrochemical cells.
  • the thickness of the electrode can be adapted to the desired objectives, the usual thicknesses when used in photoelectrochemical cells are in a range from 10 to 100 ⁇ m, preferably 20 ⁇ m.
  • the electrode arrangement preferably has a conductive layer and / or an insulating layer, the conductive layer being able to serve as an additional electrode element, while the insulating layer enables the electrode arrangement or the photoelectrochemical cell to be shielded.
  • an electrode, a membrane as an insulation layer, an electrolyte-containing counterelectrode and a photoelectrochemical cell comprising a light-absorbing layer sensitized with a dye layer comprises a counterelectrode and an electrolyte which are integrally formed and consist of a layer of an electrolyte-, carbon-containing, printable paste.
  • the carbon-containing, printable paste is produced in particular by a method as described above.
  • Such a photoelectrochemical cell is simple and inexpensive to manufacture, without having to accept a decisive loss in performance, in particular a reduced efficiency of the photoelectrochemical cell, in comparison with conventional cells.
  • the cost-benefit value of a cell according to the invention is significantly improved by the electrolyte-containing counter electrode compared to the prior art.
  • a particularly advantageous photoelectrochemical cell has an additional graphite layer on the carbon-containing paste that has been dusted on. Furthermore, the electrode and / or the combination of counter electrode and electrolyte is additionally covered with an electrically conductive layer.
  • This Electrically conductive layer can serve as an electrode element and can provide a particularly powerful electrode arrangement.
  • the photoelectrochemical cell in particular the at least one electrically conductive layer, is preferably covered with at least one insulating layer which terminate the photoelectrochemical cell from the outside.
  • a ruthenium (Ru) -containing dye is preferably used as the dye for the sensitized coloring material layer; metal, ITO or a conductive glass has proven to be advantageous as the material for the conductive layers.
  • FIG. 1 shows schematically a layer structure of an embodiment of a photoelectrochemical cell according to the invention, in which an embodiment of an electrolyte-containing counter electrode according to the invention is integrated.
  • FIG. 1 shows a preferred embodiment of cell 1 according to the invention. It is expressly pointed out that the layer thicknesses are not shown to scale, but only serve to explain and depict the basic structure.
  • the individual layers are composed as follows:
  • the TiO 2 layer is porous and has a rough surface to which a dye layer 50, also called a chromophore layer, is applied.
  • a ruthenium-containing dye was used as the dye in this embodiment.
  • the combination of the TiO 2 layer 40 and the dye layer 50 is referred to as the light-absorbing layer.
  • the second layer of the four-layer cell consists of a light-reflecting insulation layer 80 which is applied to the light-absorbing layer 40, 50 sensitized with a dye layer.
  • the third layer of the four-layer cell, the electrode-electrolyte combination layer 30, is printed directly in the form of the electrolyte-, carbon-containing, printable paste on the second layer and then with a stamp to obtain thin layers, in the insulation layer 80, with a print from about 100 to 50,000 Pa (1 to 500 g / cm 2 ).
  • Paste 30 has a proportion of 10% by weight of Degussa carbon black FW 200 and a proportion of 8% by weight of Timcal Timrex SFG 44 graphite. Before application to the light-absorbing layer 40, 50, the paste was stirred for five minutes and then 15 Minutes treated with ultrasound.
  • the fourth layer of the four-layer cell which consists of a thin graphite layer 31 comprising a few layers, is dusted onto the third layer, the printable paste 30 containing electrolyte and or carbon.
  • an ITO layer is additionally provided as the conductive carrier 20.
  • the photoelectrochemical cell described is closed on both sides by an insulating layer 60, 70.
  • the insulating layers are preferably made of transparent material, such as plastic or glass.
  • At least one of the insulating layers 60, 70 must be transparent to the light to be converted into electrical energy so that it can reach the light-absorbing layer 40, 50.
  • the insulating layer 60 is made of transparent plastic and faces the light to be converted into electrical energy
  • the insulating layer 70 is made of non-transparent plastic.

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

Abstract

L'invention concerne un procédé pour produire une pâte pouvant être imprimée, contenant un électrolyte et du carbone, se présentant notamment sous la forme d'un matériau d'électrode pour une contre-électrode contenant un électrolyte, destinée à une cellule photoélectrochimique. Ce procédé consiste à: préparer un solvant contenant des sels électrolytiques et un auxiliaire électrolytique; ajouter du noir de carbone, présentant par exemple une grande surface, et/ou un noir de carbone conducteur; ajouter du graphite, par exemple de très faible résistance de façon à produire une suspension; agiter le solvant contenant le noir de carbone et le carbone de façon à produire une suspension sensiblement homogène; traiter avec des ultrasons la suspension homogénéisée de façon à produire une pâte épaisse, pouvant être imprimée.
PCT/DE2000/002723 1999-08-11 2000-08-05 Electrode et cellule photoelectrochimique a quatre couches, procede de production d'une pate pouvant etre imprimee, contenant un electrolyte et/ou du carbone, et d'une electrode Ceased WO2001011702A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00965749A EP1125335A1 (fr) 1999-08-11 2000-08-05 Electrode et cellule photoelectrochimique a quatre couches, procede de production d'une pate pouvant etre imprimee, contenant un electrolyte et/ou du carbone, et d'une electrode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19937910.6 1999-08-11
DE19937910A DE19937910A1 (de) 1999-08-11 1999-08-11 Elektrode und photoelektrochemische Zelle sowie Verfahren zur Herstellung einer kohlenstoffhaltigen, druckfähigen Paste und einer Elektrode

Publications (1)

Publication Number Publication Date
WO2001011702A1 true WO2001011702A1 (fr) 2001-02-15

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PCT/DE2000/002723 Ceased WO2001011702A1 (fr) 1999-08-11 2000-08-05 Electrode et cellule photoelectrochimique a quatre couches, procede de production d'une pate pouvant etre imprimee, contenant un electrolyte et/ou du carbone, et d'une electrode

Country Status (3)

Country Link
EP (1) EP1125335A1 (fr)
DE (1) DE19937910A1 (fr)
WO (1) WO2001011702A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131627A1 (fr) * 2010-04-20 2011-10-27 Varta Microbattery Gmbh Électrolyte compressible

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293396A (en) * 1979-09-27 1981-10-06 Prototech Company Thin carbon-cloth-based electrocatalytic gas diffusion electrodes, and electrochemical cells comprising the same
US5525440A (en) * 1992-03-11 1996-06-11 Ecole Polytechnique Federale De Lausanne (Epfl) Method for the manufacture of a photo-electrochemical cell and a cell made by this method
US5783325A (en) * 1996-08-27 1998-07-21 The Research Foundation Of State Of New York Gas diffusion electrodes based on poly(vinylidene fluoride) carbon blends
EP0928036A1 (fr) * 1998-01-02 1999-07-07 De Nora S.P.A. Electrode à diffusion gazeuse à base de tissu de carbone pour cellule électrochimique et procédé de fabrication

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3328869A1 (de) * 1983-08-10 1985-02-28 Nukem Gmbh, 6450 Hanau Photovoltaische zelle und verfahren zum herstellen dieser
KR100220609B1 (ko) * 1989-12-27 1999-09-15 사토 토시아키 고체전해 콘덴서 및 그 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4293396A (en) * 1979-09-27 1981-10-06 Prototech Company Thin carbon-cloth-based electrocatalytic gas diffusion electrodes, and electrochemical cells comprising the same
US5525440A (en) * 1992-03-11 1996-06-11 Ecole Polytechnique Federale De Lausanne (Epfl) Method for the manufacture of a photo-electrochemical cell and a cell made by this method
US5783325A (en) * 1996-08-27 1998-07-21 The Research Foundation Of State Of New York Gas diffusion electrodes based on poly(vinylidene fluoride) carbon blends
EP0928036A1 (fr) * 1998-01-02 1999-07-07 De Nora S.P.A. Electrode à diffusion gazeuse à base de tissu de carbone pour cellule électrochimique et procédé de fabrication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131627A1 (fr) * 2010-04-20 2011-10-27 Varta Microbattery Gmbh Électrolyte compressible

Also Published As

Publication number Publication date
EP1125335A1 (fr) 2001-08-22
DE19937910A1 (de) 2001-03-15

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