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WO1996029715A1 - Methode de fabrication d'un module de cellules photoelectrochimiques presentant une stabilite de longue duree - Google Patents

Methode de fabrication d'un module de cellules photoelectrochimiques presentant une stabilite de longue duree Download PDF

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Publication number
WO1996029715A1
WO1996029715A1 PCT/CH1996/000106 CH9600106W WO9629715A1 WO 1996029715 A1 WO1996029715 A1 WO 1996029715A1 CH 9600106 W CH9600106 W CH 9600106W WO 9629715 A1 WO9629715 A1 WO 9629715A1
Authority
WO
WIPO (PCT)
Prior art keywords
module
webs
glass
chambers
glass plates
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CH1996/000106
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German (de)
English (en)
Inventor
Andreas Hinsch
Marcus Wolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecole Polytechnique Federale de Lausanne EPFL
Original Assignee
Ecole Polytechnique Federale de Lausanne EPFL
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 Ecole Polytechnique Federale de Lausanne EPFL filed Critical Ecole Polytechnique Federale de Lausanne EPFL
Priority to CH02226/97A priority Critical patent/CH693476A5/de
Priority to DE19680102T priority patent/DE19680102B4/de
Priority to AU49366/96A priority patent/AU4936696A/en
Publication of WO1996029715A1 publication Critical patent/WO1996029715A1/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
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • 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
    • H01G9/2081—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
    • 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 a long-term stable module which contains a non-heat-resistant material, in particular a sensitizer, two glass plates being connected on the circumferential side to an edge sealing structure based on glass solder and the non-heat-resistant material after a thermal Sealing of the glass plates by at least one suitably formed filling opening is pumped into the sealed module.
  • the invention further relates to a long-term stable module produced by the method.
  • a regenerative photo-electrochemical cell in which between two plates made of glass, plastic or metal interconnects, electrodes and a chroophore are enclosed.
  • the chromophore is designed as a monomolecular layer on the surface of a metal oxide semiconductor with a high inner surface.
  • the structure of such a solar cell can be compared with an electrochemical battery (galvanic cell), the one electrode (photoelectrode layer) of which is coated with a photochemically active sensitizer which absorbs sunlight.
  • the US 4,117,210 which also deals with a solar cell of the type mentioned, proposes the side edge with an inert insulation material such as. B. seal epoxy.
  • an inert insulation material such as. B. seal epoxy.
  • the non-heat-resistant sensitizer e.g. an organometallic compound
  • the edge seal is made.
  • a method for producing a sealed cell is known from JP 61-252 537. Two glass plates are coated with electrodes and then connected along the circumference with a low-melting glass. A functional high polymer material and an electrolyte are injected into the cell through an injection port. Then a polymer film is deposited electrolytically on an electrode. The discharged electrolyte solution is then pumped out and replaced by an electrolyte which does not attack the polymer film. The injection opening is closed with a silicone resin and covered with a solder.
  • Thermal sealing is also known in the case of controllable display cells (e.g. liquid crystal displays), where a liquid is enclosed between two glass plates connected by means of a low-melting glass solder (e.g. JP 56-114 922) .
  • controllable display cells e.g. liquid crystal displays
  • a liquid is enclosed between two glass plates connected by means of a low-melting glass solder (e.g. JP 56-114 922) .
  • the object of the invention is therefore to provide a module and a method for producing such a module which has or enables the long-term stability of the order of several years which is essential in practice.
  • the edge sealing structure and the webs are produced by a selective coating (one or both glass plates) based on glass solder.
  • a selective coating one or both glass plates
  • at least one of the glass plates is brought onto or above the transformation temperature of the glass.
  • the non-heat-resistant material is pumped into the sealed module through at least one suitably designed filling opening.
  • the temperature must be chosen so high that the glass of the plates becomes plastically deformable. It is only from this (transformation) temperature that it is possible to produce larger sealed modules with a minimum and constant plate spacing (leveling of the glass plates and possibly minimizing the spacing).
  • the glass plate sinks under its own weight and adapts to the other in the soft (ie tension-free) state. This enables the glass solder to be wetted and diffusion-tightly connected to both glass plates at every point of the edge structure and the webs arranged on the inside of the module.
  • the distance between the glass plates should be constant across the entire module be (otherwise the different cells have different electrical characteristics).
  • Thermal sealing processes can produce much better diffusion barriers.
  • the layer structure of the module is not completed before sealing, but rather the sealing step is introduced in a stage of the production process in which the high temperatures are permitted and the sensitive materials are only introduced into the module afterwards that have hitherto stood in the way of the use of good sealing methods.
  • the key point of the invention is therefore that a solution containing the corresponding substance (eg sensitizer, electrochromic substance etc.) is only filled after the module has been sealed / encapsulated.
  • This method offers a number of decisive production advantages compared to the known method of sensitization in the immersion bath.
  • the idea according to the invention can also be used for the production of arbitrarily sealed modules which have at least one nanoporous carrier layer on the inside with an adsorbate: the module is sealed before the adsorbate is introduced and the adsorbate is subsequently removed by a suitably designed or attached filling opening pumped in.
  • the immersion bath process for protection against water vapor, oxygen and other undesirable foreign substances has to be carried out in a protective gas atmosphere (so that no water vapor can be deposited on the layer)
  • these complex methods are largely dispensed with, as the sensitive sensitizer solution can be taken directly from the storage tank the closed (e.g. evacuated) module can be pumped.
  • the risk of contamination in the sense of undesired foreign substance adsorption
  • the sensitizer solution can also be used very sparingly in this way.
  • the thickness of the module is therefore much smaller than its transverse dimensions.
  • the method is typically applied to modules in which the thickness of the module walls is much greater than the thickness of the layered module interior.
  • the plates are preferably connected by the webs at a distance of less than 100 Jim.
  • the thermal sealing is typically carried out in the temperature-stabilized oven. Mechanical pressure can also be used to join the panels.
  • a glass with a transformation temperature in the range of 550-580 ° C. is preferably used.
  • the sealing temperature is e.g. B. in the range of 600-700 ° C.
  • the invention makes it possible to connect two large individual plates at a precise distance from one another, even if they originally had unevenness. Due to the small distances, the melted glass solder has a capillary force which forces the plates into a uniform distance of e.g. B. brings 20 microns. Another is in the area of the transformation temperature Forming or bending of the plates possible. This is of interest for vehicle technology and architectural applications (spherical, cylindrical or arbitrarily curved modules).
  • the glass soldering technique is superior to the adhesive processes based on organic or inorganic polymerizations or organic-inorganic copolymerizations with regard to long-term stability, gas tightness and vapor tightness.
  • the thermal stability is also much better, since outgassing or decomposition phenomena can occur with polymer-based adhesives even at temperatures below 100 ° C.
  • a hermetically sealed arrangement is for the life of photoelectrochemical solar modules, electrochromic modules u. Like. Of the greatest importance.
  • the sealing method according to the invention makes it possible to work with very small, closed volumes in the sensitization or activation.
  • the purity of the small solution volumes to be filled into the modules can also be lower than that of a large immersion bath without the proportion of undesirably adsorbed foreign substances being higher as a result.
  • the upstream sealing at high temperatures renders the readsorption of water vapor and other possibly harmful gases or aerosols in the highly porous Semiconductor layer (carrier layer) prevented.
  • the undesired adsorption mentioned inevitably takes place when the sintered photoelectrode layer is cooled in air and then sensitized in an immersion bath.
  • the modules according to the invention sealed at high temperatures are completely water-free due to the thermal outgassing or elimination of water and hydroxide groups after the sealing. Before being filled with the sensitizer solution, the modules can be stored closed for any length of time and do not have to be kept under protective gas.
  • the proportions of water and foreign matter in the system can therefore be kept very low with the present invention without great expenditure on production technology (ie largely without an inert gas atmosphere).
  • the webs increase the mechanical stability of the entire module and facilitate the bubble-free filling of the sensitizer solution or an electrolyte. They also have a meaning for the electrical function of the module.
  • the webs are advantageously attached in a linear manner in order to divide the interior of the module into strip-shaped chambers.
  • chamber shapes e.g. squares, honeycombs, circles
  • other chamber shapes e.g. squares, honeycombs, circles
  • the webs preferably have a width of 0.1-5 mm and a mutual spacing of 5-50 mm.
  • the webs are preferably made of the same (or a suitably modified) material as that used for sealing.
  • a plurality of linear webs also create a mechanically strong connection between the plates.
  • the webs can be applied to the plates with the aid of a screen printing process and sintered (for example together with electrodes and carrier layers applied in the same way) prior to the thermal sealing.
  • the sintering takes place - e.g. B. depending on the glass solder used - at a temperature in the range of 400-650 ° C, in particular below 600 ° C instead.
  • Both the webs and all other layers can be applied using any printing method (eg inkjet printing, gravure printing).
  • printing method eg inkjet printing, gravure printing.
  • the processes known from the production of printed circuit boards should be mentioned.
  • the composition of the glass solder during the melting process can be carried out by suitable means oxidic additives like B p O -__ PbO, Al 2 0- ,, CeO ? , Zr C> 2 'Sn0 2 , SiO-, v o 0 ⁇ ' Zn0 ' sb 2 ° V Ti0 2 and In 2 ° 3 in the form smaller Particles ⁇ 1 ⁇ m with volume fractions ⁇ 30% can be changed. In this way, the interface properties and the adhesion can also be influenced favorably.
  • the surcharges are z. B. introduced as part of the screen printing process.
  • the aggregates are not chemical constituents that are already contained in the glass solder, but are subsequently added fine-grained materials.
  • the oxidic additives mentioned are advantageously of the order of magnitude of a few nanometers ( ⁇ 100 nm, in particular in the range of approximately 10 nm) and have a very large specific surface area. They can be made hydrophobic or hydrophilic. Such particles can e.g. B. be generated by a continuous flame hydrolysis process (continuous fla hydrolysis). They can show an amorphous structure in crystallographic X-ray analysis.
  • certain webs can be produced from an insulating material (in particular glass solder) as a matrix and a conductive filler material embedded therein.
  • the filler content is preferably less than 70% by volume.
  • the grain size should be selected according to the size of the cross-section of the web and should not exceed 50 ⁇ m. It is clear that the fillers must be thermally resistant. Pigments made of mica, titanium dioxide, zirconium dioxide, silicon dioxide, graphite, carbon black, fluorine- or antimony-doped tin oxide, metal (eg titanium, aluminum) and titanium nitride are suitable for glass solders. Of course, the pigments should be much smaller than the smallest cross-sectional dimension of the web. With a plate spacing of z. B. 10-30 microns, the filler particles are typically less than 1 micron.
  • the bars with light-scattering filler particles. These particles can also be conductive, as described above.
  • the light striking the webs is coupled into the adjacent photoactive area of the module via total reflections in the glass structure, which - compared to the use of transparent web materials - results in an improvement in the light yield.
  • Stable glass solders, crystallizing glass solders or composite glass solders are used to manufacture the webs.
  • the glass solders should have a thermal expansion coefficient that is slightly below that of the glasses to be soldered.
  • a further function of the webs can be that they are made of an electrochemically resistant material and are used to cover certain layer structures (for example conductor tracks) as protection against corrosion.
  • layer structures for example conductor tracks
  • metallic conductor tracks Al conductor tracks
  • the plates have been provided with a (partially) transparent conductive layer (eg made of fluorine-doped tin oxide) (TCO layer) over the entire surface before the conductor tracks, electrodes and webs are applied.
  • TCO layer fluorine-doped tin oxide
  • the transparent conductive layer is itself divided into strip-shaped areas in accordance with the subdivision of the module interior indicated by the webs. This can e.g. B. done by scratching or etching.
  • the elongated strip-shaped regions are also divided into individual sections or partial be shared. A gap of z. B. 1 mm.
  • the webs are applied in the form of a glass solder paste to a plate prepared in this way.
  • the glass solder resp. the paste is not mixed with conductive particles.
  • the subsequent thermal sealing according to the invention at a temperature of more than 550 ° C., in particular more than 600 ° C. surprisingly leads to the webs (which are transparent according to a preferred embodiment) nonetheless providing a conductive connection between the spaced apart ones Form plates.
  • the low contact contact resistances formed in this way can possibly be attributed to the floating and mutual contacting of the tin oxide coatings in the glass solder.
  • the conductivity of the fluorine-doped tin oxide coating under the surface contact is only slightly reduced by chemical interactions with the glass solder. Tests have shown that this requires distances between the plates of less than 30 ⁇ m, in particular 25 ⁇ m and less.
  • This type of electrical connection between the plates represents a particularly simple method in terms of production technology for producing series-connected (for example Z-connected) modules.
  • the webs can (but do not have to) perform a number of different functions: sealing the interior of the module; Increasing the mechanical stability of the module; additional coupling of light into the photoactive layer; Facilitated bubble-free filling; electrical connection between the electrodes applied to different plates; mutual isolation of individual chambers of the module; Diffusion barrier against potential drift or separation problems; Corrosion protection (e.g. for conductor tracks).
  • the smallest possible distance between the electrodes is required to achieve a small series resistance in the electrolyte (or in the organic conductor of an electrochromic module).
  • both electrode coatings are applied to glasses, it is possible with the proposed method to seal at temperatures that are slightly above the transformation temperature of the glasses. A leveling of the glasses and thus of the electrodes then takes place due to the reduction of the glass voltage. The leveling effect can be increased by applying mechanical pressure to the glasses from outside.
  • glass solders as the material of the webs, there are also strong capillary forces after melting the solders and the liquid connection to the opposite contact point, which cause the electrodes to be leveled further.
  • a nanoporous layer can be applied to the inside of the module, the effective inner surface of which is at least a factor of 100, in particular a factor of 500 and more equivalent.
  • the sensitizer introduced in dissolved or suitably dispersed form is deposited on this layer.
  • the nanoporous layer consists, for. B. from a semiconducting, as transparent as possible material (z. B. Titanium dioxide) with a very high internal surface to adsorb the largest possible amount of sensitizer.
  • a sensitizer z. B. a metallic organic dye can be used. However, purely organic dyes or highly absorbing semiconductor clusters (“quantum dots”) can also be used.
  • the sensitizer ( adsorbate) z. B. pumped into the module in the form of a colloidal solution. Pumping in the form of a supersaturated solution is also conceivable.
  • drainage channels can be provided (inside the module), which preferably have a cross section of not more than 0.5 mm ⁇ 0.5 mm. Due to the capillary forces, the pumped solution is quickly distributed.
  • the drainage channels can e.g. B. mechanically (milling, sandblasting), chemically (by etching) or physically (z. B. by laser radiation).
  • the glass plates provided with a transparent conductive layer can be provided with a mask using the screen printing method and the areas left free from the mask can be etched or sandblasted.
  • the drainage channels can also help to stabilize the module (in particular to separate the electrolyte from the webs). This is the case if the nanoporous layer (in the area of which the electrolyte is ultimately required and desired) through the drainage channels from the webs or. is separated from other cells and if the The amount of electrolyte is such that it is sufficient to fill the capillary space between the nanoporous layer and the counter electrode.
  • the thickness of the chambers ie the distance between the nanoporous layer and counterelectrode
  • the capillary forces draw the electrolyte into the "electrically active" area of the photoelectrochemical cell.
  • conductor tracks and electrodes are also applied on the inside of the module using thin-film technology, drainage channels and conductor tracks or electrodes preferably being aligned with one another in such a way that the drainage channels additionally act as insulating separating areas at the desired locations (mechanical interruption of the electrically conductive coating of the Plates).
  • the counterelectrode can either be arranged on the electrically conductive (or possibly electrically coated) back cover (which may be covered with a thin catalyst layer), or - in a one-sided layer structure - by an electrically insulating po ⁇ eyed spacer (spacing layer) from the photoelectrode ge.
  • Either a liquid electrolyte (eg with an iodine / iodide redox pair), a solid or gel electrolyte or an organic (or partially organic) conductor polymerized from a liquid phase can be used for the charge transport between the electrodes.
  • the electrode coatings can be applied using screen or other printing processes. This is followed by consolidation by thermal sintering at z. B. 300-550 ° C.
  • a particularly preferred possibility for introducing an adsorbate (sensitizer, electrochromic substance) into a nanoporous layer is characterized in that the adsorbent is dispersed in the form of stabilized colloids in a solvent and essentially that of the nanoporous layer volume of the solvent to be adsorbed is brought onto the nanoporous layer in order to enable the time-delayed adsorption of the adsorbate.
  • the desired amount of the solution can first be completely pumped into the module and distributed there before the deposition on the nanoporous layer begins.
  • essentially the volume of solvent corresponding to the module volume is used as the transport medium.
  • variants are also conceivable in which a much larger volume of solution is pumped through the module ("continuous filling"). In both cases, the discharged solvent has to be pumped out and replaced by the electrolyte.
  • a drying rinse or vacuum drying can be interposed to eliminate undesired solution residues.
  • the time-delayed adsorption can be achieved by creating a colloid solution.
  • the adsorbate can be transported in the solution in an amount which exceeds the saturation limit of a molar solution many times over. Stabilizing the
  • Colloids require that the solubility of the adsorbate mo-
  • the time delay according to the invention therefore means that the Time that is required to distribute the colloidal solution on the surface to be coated (eg in a sealed electrochemical cell) is negligible compared to the time within which a substantial part of the colloids is dissolved.
  • the adsorption of the adsorbate can be initiated by irradiation of destabilization energy (heat radiation, laser radiation, ultrasound or the like) or application of an electrical voltage as soon as the colloidal solution is evenly distributed on the nanoporous layer .
  • destabilization energy heat radiation, laser radiation, ultrasound or the like
  • an electrical voltage as soon as the colloidal solution is evenly distributed on the nanoporous layer .
  • the adsorbate is advantageously stabilized or coadsorbated. microencapsulated.
  • the destabilizing energy should not cause the solvent to evaporate. Rather, it is about transferring the adsorbate to the nanoporous layer.
  • a particularly preferred embodiment is characterized in that the electrolyte which is to be introduced into the module anyway is chosen as the solvent for sensitizer pigments or other nanodisperse substances. That is, Sensitizer and electrolyte can be filled in in one step.
  • the module can be temporarily sealed and temporarily stored until the sensitizer is adsorbed by the nanoporous layer. In a sense, it is a "discontinuous variant".
  • it may be necessary or advantageous to provide in the module, but outside the module chambers and only with reservoir areas connected to them.
  • the reservoir areas can be designed as wide, deep drainage channels.
  • the loading of the nanoporous layer with the sensitizer takes place due to the concentration gradient by slow diffusion from the reservoir areas into the module chambers.
  • the relationship The reservoir volume, the sensitizer concentration and the module chamber length are expediently chosen so that the electrolyte solution is as free of sensitizer as possible after the loading process has ended.
  • the reservoir areas can be pumped out again after a certain time and filled with a chemically inert filler.
  • a variant of the one-step process is its repetition. a colloidal solution is pumped into the PEC cell, discharged by irradiation of destabilizing energy and pumped out, this process being repeated several times.
  • the electrolyte remaining in the reservoir area and in the drainage channels of the module chambers can be pumped away after completion of the module activation and / or by a sealing compound (e.g. an epoxy resin based on silicone or a silicone oil) or by a protective gas (argon, Nitrogen etc.) can be partially or completely replaced.
  • a sealing compound e.g. an epoxy resin based on silicone or a silicone oil
  • a protective gas argon, Nitrogen etc.
  • Bilizer solution for rapid adsorption on only part of the photoelectrode and the outflow of sensitizer-free solvent (chromatographic effect). For uniform dyeing, it is then necessary to force the sensitizer to actively transport the substance through the module by repeatedly pumping through the solution.
  • a sensitizing or activating solution is a colloid-disperse solution in which the sensitizer or the electrochromically active substance is stabilized.
  • This can be done by ionic and non-ionic detergents or amphiphilic substances and stabilizing aids, such as fatty acids or fatty acid derivatives, alkyl or arylsulfonic acid esters, alkyl or arylsulfonic acid derivatives, alcohol ether sulfates, phosphoric or phosphoric acid derivatives, alcohols or polyols, salts with cations of the classes tetraalkylammonium, alkylimidazolium, piperazinium and tetraalkylphosphonium, sulfobetaines, phospho- or phosphonatobetaines, partially or perfluorinated hydrocarbons or derivatized siloxanes with terminal reactive or ionophoric groups.
  • the stabilized sensitizer can be present in addition to other substances required for electrochemical activ
  • the chemisorption of the sensitizer or. electrochromically activatable substance on the nanoporous layer prevented or greatly delayed. As already mentioned above, this allows the modules to be filled without any instantaneous adsorption of the sensitizer (or electrochromically activatable substance).
  • the detergents and stabilization aids can simultaneously act as electrochemically functional auxiliary coadsorbates. The mass transfer takes place from the layered module interior to the nanoporous layer (photoelectrode).
  • the components necessary for producing an electrochemical contact, such as the redox mediator, remain in the module volume, so that the module can be activated in a single step (“discontinuously”).
  • the circuitry structure and the geometric arrangement can be carried out in a manner known per se. If the module is divided into a regularly arranged two-dimensional arrangement of chambers by means of webs, then it is advantageous to choose a combination of Z and P interconnection.
  • the chambers can e.g. B. P-connected in columns and Z-connected in rows. In the case of smaller modules, pure Z or P interconnections can also be useful.
  • FIG. 2 shows a schematic illustration of a module in cross section, which has a plurality of Z-connected chambers and provided with drainage channels;
  • FIG. 3 shows a schematic representation of a section through a module with a one-sided Z connection
  • Figure 4 is a schematic representation of a section through a module with P-interconnection.
  • Figure 5 is a schematic representation of a section through a module with one-sided P-connection and tapping on both sides.
  • FIG. 6 shows a schematic illustration of a section through a module with W connection
  • FIG. 7 shows a schematic illustration of a plan view of a module with a combined Z and P interconnection
  • FIG. 8 shows a schematic perspective illustration of section AA according to FIG. 7
  • FIG. 9 shows a schematic perspective illustration of section BB according to FIG. 8;
  • FIG. 10 shows a schematic illustration of a voltage-connected module in plan view
  • FIG. 11 shows a schematic illustration of a subdivision according to the invention of the transparent conductive layer within the cells.
  • FIG. 1a-g schematically shows the most important process steps for producing a photoelectrochemical module (PEC module).
  • TCO Transparent Conductive Oxide
  • An example of a TCO layer 3, 4 is a pyrolytically applied, fluorine-doped tin oxide with a thickness of e.g. B. 0.1-1.0 ⁇ m.
  • the glass plates 1, 2 have e.g. B. a thickness of 1-6 mm. They represent walls of the PEC modules.
  • drainage channels 7.1, 7.2, 7.3, respectively. 8.1, 8.2, 8.3 attached In Fig. 1a it is indicated schematically that suitable masks 5, 6 are applied to the TCO layers 3, 4. Subsequent sandblasting results in the desired drainage channels 7.1,..., 7.3 and, respectively, at the locations not covered by the masks 5, 6. 8.1, ..., 8.3 (Fig. 1b). Then the masks 5, 6 are removed again (FIG. 1c).
  • the drainage channels have a width and a depth of preferably less than 0.5 mm each. You are at a distance of z. B. 5 mm.
  • FIG. 1d the actual circuit structure is built up (Fig. 1d).
  • webs 10.1, 10.2, 10.3 respectively. 11.1, 11.2, 11.3 immediately next to the drainage channels 7.1, ..., 7.3 respectively. 8.1, ..., 8.3 applied.
  • a nanoporous layer 9.1, 9.2, 9.3 e.g. a Ti0 2 layer and a Ge gene electrode coating 14.1, 14.2, 14.3 applied. This happens e.g. B. with screen printing.
  • the webs 10.1, ..., 10.3, 11.1, ..., 11.3, the nanoporous layer 9.1, ..., 9.3 and the counter electrode coating 14.1, ..., 14.3 are z.
  • the two glass plates 1, 2 with the coated sides are placed against each other.
  • the webs 10.1, ..., 10.3 »of one glass plate 1 come to rest on the webs 11.1, ..., 11.3 of the other glass plate 2.
  • the two glass plates 1, 2 are connected at a temperature of more than 500 ° C (e.g. at about 650 ° C).
  • the leading areas 15.1 and 16.1 respectively. 15.2 and 16.2 respectively 15.3 and 16.3 form a continuous contact between the two glass plates 1 and 2.
  • Solution 13 can contain the dye particles required for activating or sensitizing the module in microencapsulated form.
  • the colloidal solution is z. B. destabilized by irradiation of light, so that the dye particles can be deposited on the nanoporous layer 9.1, ..., 9.3.
  • the microencapsulated dye can be adsorbed on the large surface of the nanoporous layer by chemical or physical sorption and distributed as a monomolecular layer on the surface by diffusion processes.
  • the discharged solvent can now be pumped out of the module to make room for an electrolyte solution.
  • the electrolyte solution can be enclosed in the chambers 12.1, 12.2 in liquid, gelled or solid form.
  • the filler openings can then be sealed.
  • the Gelie ⁇ gelation. Solidification can be based on an induced polymerisation reaction (heating, radiation).
  • the polymerization can be selectively restricted to the individual chambers (or cell areas) by masking. If desired, unpolymerized or other residues of the electrolyte solution can be pumped out of the module prior to sealing and replaced by a chemically inert filler (inert gas, silicone).
  • colloidal solution can simultaneously be used as an electrolyte. There is then no need to pump out the solvent and subsequently pump in the electrolyte. It is basically a "1-step process" (electrolyte and dye are introduced in one step).
  • the two glass plates 1 and 2 are at a mutual distance of z. B. 20 microns.
  • the module is divided into a plurality of chambers 12.1, 12.2,... Of the same type.
  • Each chamber has e.g. B. a width of 3 mm. They are separated from one another by webs of glass solder.
  • the drainage channels 7.1, ..., 7.3 respectively. 8.1, ..., 8.3 subdivide the TCO layers 3, 4 in the desired manner (i.e. corresponding to the chambers) into electrically insulated subregions.
  • each web has a central conductive area 17.2 and two insulating areas covering it. areas 17.1 and 17.3.
  • the conductive region 17.2 connects the TCO layer 3 of one glass plate 1 with the TCO layer 4 (of the adjacent chamber or cell) of the second glass plate 2.
  • the photoelectrode (9.4) of the one chamber is thus electrically connected to the counter electrode ( 14.3) connected to the other chamber, which leads overall to a series connection of the individual chambers 12.1, 12.2, ....
  • the interconnection of the module shown in FIG. 2 is referred to as a Z interconnection for obvious reasons.
  • the drainage channels 7.1, ..., 7.3 and 8.1, ..., 8.3 facilitate the rapid drawing in of the colloidal solution, respectively. the electrolyte / dye mixture into the chambers. This is explained in more detail below.
  • the conductive region 17.2 represents a part of the web which, due to suitable filler particles, has a relatively high conductivity. Instead of specifically increasing the conductivity in the central area 17.2, it can be lowered in a targeted manner in the outer areas 17.1 and 17.3 if the web material is sufficiently conductive (e.g. by means of mica).
  • the direction of incidence of the light is identified by the arrows drawn in bold.
  • the photoelectrode layer typically consists of transparent semiconducting nanopigments (10-50 nm) with a high surface area.
  • the photoelectrode layer is preferably applied using screen printing technology (in a thickness of approximately 5-15 ⁇ m) and - as already mentioned - sintered. Sintering creates the nanoporous layer with an effective geometric surface with a factor of 500 or more.
  • the counter electrode coating 14.3 is a catalytically effective coating of the (semi-) transparent TCO layer and consists, for. B. essentially from platinum, palladium, ruthenium oxide or the like. It is a very thin ( ⁇ 20 nm) coating with high catalytic effectiveness with good mechanical adhesion and good transparency. You can z. B. by pyrolytic decomposition of platinum compounds which are dissolved or dispersed in a screen-printable or sprayable medium. A further possibility is the dispersion of platinum nanoparticles or the dispersion of platinum deposited on oxidic nanoparticles (eg tin oxide, titanium oxide etc.) in the media mentioned. The coating is applied by spraying or screen printing and sintered.
  • the TCO layers 3 and 4 can be doped differently and to different degrees (in order to achieve a higher conductivity of the TCO layer 4, for example).
  • the webs between the chambers can be designed in different ways.
  • a preferred variant is e.g. B. in that the web is completely conductive. It then consists of a material such as B. glass solder with corrosion-resistant filler (corrosion resistance compared to the electrolyte).
  • As a filler such. B. graphite powder, Sn0 2 : F, Sn0 2 : Sb powder or Sn0 2 : Sb-coated mica pigments and similar (sometimes commercially available) products in question.
  • the volume fraction of the filler can make up to 70%. With a web thickness of 10-20 ⁇ m and a web width of 2 mm or less, this results in a largely planar (or line-shaped) contact between the TCO layers 3 and 4.
  • the electrical insulation continues to be guaranteed through the drainage channels 7.1, ..., 8.3.
  • fully or area-conducting webs can be achieved in that stable glass solders (ie those which do not change their structure during melting and can therefore be repeatedly melted) or crystallizing glass solders (those when heated) crystallize to the soldering temperature) without filler particles which increase conductivity (ie in quasi-pure form) are selectively applied to the TCO layers in accordance with the desired webs and are melted and sealed in the region of the transformation temperature of the glass plates 1, 2. It has been shown that such soldering leads to electrically conductive webs, although the base material (glass solder) is actually not conductive.
  • FIG. 2 A further variant of FIG. 2 consists in that the drainage channels are dispensed with and, on the one hand, the insulating region 17.1 of the web is pulled through the TCO layer 3 to the glass plate 1 and, on the other hand, the non-conductive region 17.3 is pulled through the TCO layer 4 onto the glass plate 2. In this way, the TCO layers 3, 4 are again Cd in the desired manner. H. divided according to the division and geometry of the individual chambers).
  • FIG. 3 shows a variant of the Z interconnection. It is a so-called one-sided Z connection, since all layers are arranged on the same glass plate 18.
  • the second glass plate 19 is used exclusively for sealing the module. It is held at a distance from the glass plate 18 by insulating webs 20.1, 20.2, 20.3. Immediately on the glass plate 18 are - corresponding to the chambers
  • Spacer layers 23.1, 23.2, 23.3 are provided on the photoelectrode layers 22.1, 22.2, 22.3, on which finally the counter electrode layers 24.1, 24.2, 24.3 are arranged.
  • the electrolyte is also located in the spacer layers 23.1, 23.2, 23.3.
  • the distance between the photo and counter electrode layer 22.1, respectively. 24.1 is determined by the spacer layer 23.1 and not by the distance between the glass plates 18 and 19, the planarity of the glass plates 18, 19 is not critical. Surface unevenness in the range of 50 ⁇ m can be tolerated here. That is, it is not mandatory to work in the area of the transformation temperature of the glass plates. Furthermore, the use of expensive polished glass plates can also be dispensed with. It is possible to work with ordinary float glass. The insulation bars are then also applied in greater thickness (e.g. 20-200 ⁇ m).
  • the spacer layers 23.1, 23.2, 23.3 consist of porous, light-scattering (and of course electrically insulating) transparent pigments.
  • the size of the pigments moves e.g. B. in the range between 100 and 1,000 nm. B. 5 microns. Layers of titanium dioxide, aluminum oxide, zirconium oxide, silicon oxide, mica etc. are suitable.
  • As an inorganic adhesion promoter between the pigment particles e.g. B. nanoparticles or thermally decomposable compounds of said oxides (and tin oxide) are used, which are added in a quantity of up to 15% by volume.
  • the counter electrode layer, the z. B. has a thickness of 5-50 microns can be formed by a porous graphite layer.
  • the catalytic activity is achieved by admixing z. B. soot or platinum nanoparticles achieved (volume fraction up to 50% or up to 1%).
  • a combination layer (stack) of catalytically highly active, thin porous graphite layer and highly conductive, thicker, inactive graphite layer is also conceivable.
  • the above-mentioned nanoparticles and compounds can be used as adhesion promoters between the particles of the graphite layer.
  • a metal plate can also be used in this one-sided connection. As in FIG. 2, the incidence of light is shown by bold arrows.
  • Fig. 4 shows a schematic representation of a module in P-connection.
  • the glass plates 27, 28 are completely covered on the inside with TCO layers 29, 30.
  • a plurality of webs 31.1, ..., 31.3 divides the intermediate space between the glass plates 27 and 28 into a plurality of chambers 32.1, ..., 32.3.
  • Each of these chambers 32.1, ..., 32.3 has a photoelectrode layer 33.1, ..., 33.3 (on the TCO layer 29) and a counter electrode coating 34.1, ..., 34.3 (on the TCO layer 30).
  • Between the photo and counter electrode layer 33.1,... 34.1, ... is the electrolyte.
  • conductor tracks 35.1, ..., 35.3 and 36.1, ..., 36.3 are provided along the chambers 32.1, ..., 32.3. They exist e.g. B. made of silver. So that they are not dissolved by the electrolyte, they must be covered against it. In the present example, this is achieved in that the webs 31.1, ..., 31.3 (which consist of an insulating, corrosion-resistant material such as glass solder, for example) have the aforementioned conductor tracks 35.1, ..., 35.3, 36.1 , ..., 36.3 completely cover. That is, the conductor tracks are attached under the webs. They can be applied using screen printing technology and then baked (Ag, Al, Cu frit).
  • FIG. 5 shows a one-sided P-connected module with taps.
  • This embodiment represents the application of the one-sided technology according to FIG. 3 to the P-connection according to FIG. 4.
  • the glass plate 37 carries the electrochemically active layers, while the glass plate 38 is used only for current tapping from the counter electrode.
  • only one of the two glass plates namely the lower glass plate 37 in FIG. 5 is provided with a TCO layer 39.
  • the glass plate 38 is also TCO-coated.
  • the two glass plates 37 and 38 are separated by webs 40.1, ..., 40.3 at a mutual distance of z. B. kept 20-200 microns.
  • the webs 40.1, ..., 40.3 also divide the interior of the module into a plurality of similar chambers 46.1, ..., 46.3.
  • Each chamber 46.1, ..., 46.3 is provided with a TiO 2 layer 43.1, ..., 43.3 (on the TCO layer 39), a spacer layer 44.1, ..., 44.3 and a counter electrode layer 45.1 arranged thereon. ..., 45.3.
  • the three layers mentioned can be designed in the same way as in the one-sided Z connection according to FIG. 3.
  • a conductor track 41.2 is arranged on the TCO layer 39 under every second web 40.2.
  • the webs 40.2 mentioned are completely insulating and completely cover the conductor track 41.2.
  • the other webs 40.1, 40.3 each have a conductive area 42.1, 42.3. This extends in each case from the height of the counter electrode layer 45.1, ..., 45.3 to the covering glass plate 38. They connect the counter electrode layers 45.1, ..., 45.3 to the ones on the glass plate 38, below the conductive areas 42.1, 42.3 of the webs 40.1 , 40.3 provided (and covered by them) conductor tracks 41.1, 41.3. The current can therefore be led away from the counterelectrode layers 45.1,..., 45.3 via the conductive regions 42.1, 42.3 and the conductor tracks 41.1, 41.3.
  • conductive areas 42.1, 42.3 must be resistant to attacks by the electrolyte.
  • These conductive areas are preferably produced by means of a glass solder with conductive admixture (eg with graphite particles).
  • each web (corresponding to the P circuit according to FIG. 4) is equipped on both sides with a conductor track.
  • it must then be possible to limit the conductive area 42.1, 42.3 so that the webs 40.1, ..., 40.3 do not become continuously conductive (short circuit).
  • the two glass plates 47, 48 which are provided on the inside with TCO layers 49, 50, are by webs 51.1, ..., 51.3 and a thickness of z. B. 10-20 microns connected.
  • the webs 51.1, ..., 51.3 are respectively covered by the TCO layers 49. 50 through to the glass plate 47 respectively. 48 led.
  • the separation points 52.1, ..., 52.3 are alternately at the lower (webs 51.1 and 51.3) and at the upper end (52.2) of the webs.
  • the photoelectrode layers 55.1,..., 55.3 are also alternately attached to the upper and lower glass plates 48 and 47 (or their TCO layers 50 and 49). The same applies vice versa for the counter electrode coatings 54.1, ..., 54.3.
  • the current therefore flows e.g. B. first through the TCO layer 49 (on the right side of FIG. 6), then through the chamber 53.3 into the TCO layer 50. He then gets into the chamber 53 and changes the side again to the TCO layer 49. It passes under the web 51.2 into the chamber 53.1 and here changes the side again.
  • the webs 51.1,..., 51.3 in the W connection are completely insulating. The current therefore does not change sides between the chambers (i.e. in the webs) but in the chambers.
  • FIG. 7 shows a partial plan view of a module with a combined Z and P connection.
  • a large number of chambers 56.11,..., 56.35 arranged in rows and columns are designed in the manner already described several times (photoelectrode, counterelectrode, electrolyte).
  • the special feature of the present embodiment is that the modules 56.11, ..., 56.15, respectively. 56.21, ..., 56.25 respectively. 56.31, ..., 56.35 are P-connected in columns. The various columns are Z-connected to one another.
  • An end tap 57 is located at the extreme end of the module. It is a relatively wide conductor track that can be contacted from the outside in order to connect the entire module, indicated as indicated, to a similar module or to an electrical circuit.
  • the end tap 57 extends in the column direction over the entire width of the module. Thin, finger-like conductor tracks 58.1, ..., 58.5 run away from it. They reach like a comb between the chambers 56.11, ..., 56.15. In the present example, they are attached to the lower glass plate 64 (cf. FIG. 8, which shows the section AA).
  • a drainage channel 61.1 is provided in the upper glass plate 65. It also extends in the column direction, ie parallel to the end tap 57 over the entire module.
  • a second drainage channel 62.1 delimits the chambers 56.11, ..., 56.15 on the opposite narrow side.
  • the drainage channel 62.1 (as can be seen in FIG. 9) is provided in the lower glass plate 64. It runs parallel to the drainage channel 61.1 and, like this, connects the P-connected chambers 56.11, ..., 56.15.
  • Z connection 59 between the chambers 56.11, ..., 56.15 and 56.21, ..., 56.25. It is a conductor track running in the column direction, which conductively connects the lower glass plate 64 to the upper 65.
  • Finger-shaped conductor tracks 60.1, ..., 60.5 run from the Z connection to the left between the chambers 56.11, ..., 56.15. They are attached to the upper glass plate 65 (and overlap in the illustration according to FIG. 7 with the conductor tracks 58.1,..., 58.5 on the lower glass plate 63).
  • the finger-like conductor tracks 60.1, ..., 60.5 extend to the drainage channel 61.1. Analogously, the conductor tracks 58.1, ..., 58.5 extend to the drainage channel 62.1.
  • Conductor tracks 63.1, ..., 63.5 run away from the Z connection 59 to the right. They are attached to the lower glass plate 64 (cf. FIG. 9) and extend between the chambers 56.21, ..., 56.25 through to the drainage channel 62.2.
  • the drainage channel 61.1 is, of course, on the upper glass plate 65 (ie it does not interfere with the course of the conductor tracks 63.1, ..., 63.5).
  • the chambers 56.21, ..., 56.25 and 56.31, ..., 56.35 are connected, the drainage channels 62.2 and 63.1 are arranged analogously to the drainage channels 62.1 and 61.2.
  • FIG. 8 shows the end of the finger-like conductor track 60.1, which comes from the Z connection 59 (cf. FIG. 7).
  • FIG. 9 shows the section BB from FIG. 7 in a three-dimensional representation.
  • the drainage channels 62.1 and 61.2 can be seen, which are in the lower resp. upper glass plate 64 respectively. 65 are embedded and the TCO layer 66 resp. 67 interrupt specifically.
  • the Z connection 59 can be seen, which z. B. connects the conductor 60.1 of the upper glass plate 65 with the conductor 63.1 of the lower glass plate 64. It can be seen from FIG. 9 that a structure according to FIG. 2 is realized in a section parallel to the conductor tracks 60.1 to 60.5 across the entire module.
  • the cells shown in cross section in FIGS. 2 to 6 are generally elongated strips (as can be seen in FIG. 7). However, these strips are advantageously also subdivided into partial areas. In principle, this will be explained with reference to FIG. 11.
  • the generally full-surface coating of the glass plate with a transparent conductive oxide is therefore not only separated by drainage channels 86, 87, 88 next to the webs 83, 84, 85, but also within a chamber into several partial areas 80.1 to 80.4 resp. 81.1 to 81.4 resp. 82.1 to 82.4.
  • the individual partial areas 80.1 to 82.4 are z. B. square. Between the partial areas 80.1, 80.2, 80.3, 80.4 (which overall correspond, for example, to the area 56.11 in FIG.
  • the width of an incision is a multiple (e.g. 10-50 times) of the distance between the glass plates.
  • 10 shows a module with a Z-connection.
  • a plurality of stripe-shaped functionally identical chambers 69.1, 69.2, 69.3 form the This is located between two glass plates and is laterally hermetically sealed by a web structure 70 which surrounds the chambers 69.1, 69.2, 69.3.
  • the chambers 69.1, 69.2, 69.3 are delimited from one another by linear webs 71.1, 71.2.
  • a Z connection 72.1, 72.2 is accommodated in the webs 71.1, 71.2 (cf., for example, conductive region 17.1 in FIG. 2).
  • a drainage channel 77.1, 77.2 is provided along one of the two long sides of each chamber 69.1, 69.2.
  • a connecting channel 73, 74 which extends transversely to the longitudinal direction of the chambers 69.1, 69.2, 69.3. It stands above a reservoir area 75.1, ... respectively. 76.1, ... in connection with each chamber 69.1, ... and their drainage channel 77.1.
  • Each connecting channel 73, 74 preferably has two filling openings 78.1, 78.2 respectively provided at the ends. 79.1, 79.2.
  • the module is sealed before the sensitizer is introduced into the nanoporous layer (eg titanium dioxide layer).
  • the module is therefore thermally sealed (e.g. according to the preferred glass solder seal) and must now be filled.
  • the interior of the module is evacuated via the filling openings 78.1, 78.2, 79.1, 79.2.
  • a colloidal solution is then pumped in, which removes the sensitizer in a colloid-stabilized form. holds.
  • the solution flows through the connecting channels 73, 74, the reservoir areas 75.1, ..., 76.1, ... into the drainage channels 77.1, ... and the chambers 69.1, ....
  • the drainage channels 77.1, ... enable a rapid distribution of the colloidal solution in all chambers 69.1, ....
  • the aim is that the nanoporous layers in the chambers 69.1, ... are completely covered with the solution before the colloidal dispersions Dye particles can be adsorbed.
  • Dye particles can be adsorbed.
  • the reservoir areas 75.1,..., 76.1 can supply dye particles (via diffusion) as long as the nanoporous layer is not "saturated".
  • the photoelectrode When the adsorption process is complete, i. H. the photoelectrode is colored, then the (completely or partially) discharged solvent, which is located in the connecting channels 73, 74 and the reservoir areas 75.1, ..., 76.1, is pumped out. An electrolyte solution is then pumped in. So that the Z-connected chambers are electrochemically separated, no electrolyte may be present in the connecting channels 73, 74. To ensure this, the two channels are preferably pumped out. filled with an inert filler (silicone). Then the filling openings 78.1, 78.2, 79.1, 79.2 are finally sealed.
  • an inert filler silicone
  • the dyes, for. B. are microencapsulated dispersed in an electrolyte.
  • the dye and electrolyte can then be introduced into the module in one step.
  • the amount of dye per m 2 of a nanoporous layer eg TiO 2 layer
  • the required amount of dye per unit volume can be determined in mol / 1 or g / 1 on the basis of the specified line or chamber volume.
  • the predetermined minimum distance between the electrodes ie the free chamber volume results in a maximum permissible particle diameter.
  • the necessary number of particles and the free particle surface can be calculated from the molecular weight and density of the dye and from the particle radius.
  • the space required for the desired surfactants and dispersion auxiliaries on the surface of the particle to be stabilized as a colloid can be determined by the number of particles and thus the concentration of the surfactants or. Dispersion aids are determined per unit volume.
  • NMO - dye cis-di (thiocyanato) bis (2, 2'-bipyridyl-
  • the described embodiments can be modified in different ways.
  • the invention is not restricted to a specific type of connection.
  • the material specifications are also not to be interpreted as restrictive for the invention.
  • the person skilled in colloid chemistry can disperse or disperse almost any sensitizer, electrochromic or other material as a nanoparticle colloid. stabilize.
  • suitable coadsorbates can also be found, which can also be used as microencapsulation for the adsorbate.
  • the invention has created the possibility of producing modules with long-term stability. The process is simplified in particular in the industrial (ie large-scale) production of plate-shaped modules.

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Abstract

Cette invention concerne une méthode de fabrication d'un module de cellules photoélectrochimiques présentant une stabilité de longue durée et contenant un matériau non résistant à la chaleur, notamment un photosensibilisateur. Deux disques de verre (1, 2) sont assemblés sur leur pourtour par une structure de scellement de bords à base de verre d'apport de brasage. Le matériau non résistant à la chaleur est ultérieurement (c'est-à-dire après le scellement thermique des disques à verre) injecté dans le module scellé par pompage via au moins un orifice de remplissage (78.1) conçu de façon adaptée. Un revêtement sélectif à l'aide de verre d'apport de brasage permet de réaliser des nervures linéaires (10.1, 10.2, 10.3, 11.1, 11.2, 11.3) pour créer des chambres de séparation. Lors de l'assemblage dans le cadre du scellement thermique, au moins un des disques de verre est amené à une température voisine de ou supérieure à la température de transformation de ce disque de verre afin d'égaliser les disques de verre (1, 2) ou de réduire la distance les séparant.
PCT/CH1996/000106 1995-03-23 1996-03-21 Methode de fabrication d'un module de cellules photoelectrochimiques presentant une stabilite de longue duree Ceased WO1996029715A1 (fr)

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CH02226/97A CH693476A5 (de) 1995-03-23 1996-03-21 Verfahren zum Herstellen eines langzeitstabilen Moduls von photoelektrochemischen Zellen.
DE19680102T DE19680102B4 (de) 1995-03-23 1996-03-21 Verfahren zum Herstellen eines langzeitstabilen Moduls von photoelektrischen Zellen
AU49366/96A AU4936696A (en) 1995-03-23 1996-03-21 Method of manufacturing a module of photoelectrochemical cells with long-term stability

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CH83295 1995-03-23

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000048212A1 (fr) * 1999-02-08 2000-08-17 Kurth Glas + Spiegel Ag Cellule photovoltaique et procede de fabrication de ladite cellule
NL1020744C2 (nl) * 2002-06-04 2003-12-08 Stichting Energie Vloeistofhoudend fotovoltaïsch element.
EP1213775A3 (fr) * 2000-12-07 2003-12-10 Seiko Epson Corporation Cellule solaire à l'état solide sensibilisée par un colorant
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US7341774B2 (en) 2000-05-30 2008-03-11 The Penn State Research Foundation Electronic and opto-electronic devices fabricated from nanostructured high surface to volume ratio thin films
US7351907B2 (en) 2002-01-25 2008-04-01 Konarka Technologies, Inc. Displays with integrated photovoltaic cells
US7414188B2 (en) 2002-01-25 2008-08-19 Konarka Technologies, Inc. Co-sensitizers for dye sensitized solar cells
EP1548868A4 (fr) * 2002-10-03 2009-08-12 Fujikura Ltd Substrat d'electrode, element de conversion photoelectrique, substrat en verre conducteur et leur procede de production, et cellule solaire de sensibilisation pigmentaire
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WO2010089263A3 (fr) * 2009-02-06 2010-11-18 Bangor University Cellule solaire à pigment photosensible
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EP2276105A4 (fr) * 2008-04-28 2012-10-03 Fujikura Ltd Module de transducteurs photoélectriques
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117210A (en) * 1977-01-27 1978-09-26 Optel Corporation Photogalvanic cell having transparent photoactive TIO2 thin film
JPS56114922A (en) * 1980-02-15 1981-09-09 Dainippon Printing Co Ltd Manufacture of liquid-crystal cell
JPS61252537A (ja) * 1985-05-02 1986-11-10 Matsushita Electric Ind Co Ltd 機能素子の製造方法
EP0333641A1 (fr) * 1988-02-12 1989-09-20 Ecole Polytechnique Féderale de Lausanne (EPFL) Cellule photoélectrochimique, procédé de fabrication d'une telle cellule et utilisation de la cellule
WO1993019479A1 (fr) * 1992-03-26 1993-09-30 Asulab S.A. Cellule photoelectrochimique regeneratrice transparente
DE4225576A1 (de) * 1992-08-03 1994-02-10 Abb Patent Gmbh Photoelektrochemische Zelle

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0815097B2 (ja) * 1990-04-17 1996-02-14 エコール・ポリテクニツク・フエデラール・ドウ・ローザンヌ 光電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117210A (en) * 1977-01-27 1978-09-26 Optel Corporation Photogalvanic cell having transparent photoactive TIO2 thin film
JPS56114922A (en) * 1980-02-15 1981-09-09 Dainippon Printing Co Ltd Manufacture of liquid-crystal cell
JPS61252537A (ja) * 1985-05-02 1986-11-10 Matsushita Electric Ind Co Ltd 機能素子の製造方法
EP0333641A1 (fr) * 1988-02-12 1989-09-20 Ecole Polytechnique Féderale de Lausanne (EPFL) Cellule photoélectrochimique, procédé de fabrication d'une telle cellule et utilisation de la cellule
WO1993019479A1 (fr) * 1992-03-26 1993-09-30 Asulab S.A. Cellule photoelectrochimique regeneratrice transparente
DE4225576A1 (de) * 1992-08-03 1994-02-10 Abb Patent Gmbh Photoelektrochemische Zelle

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ASHOKKUMAR M ET AL: "Semiconductor sensitization by RuS/sub 2/ colloids on TiO/sub 2/ electrodes", CHEMICAL PHYSICS LETTERS, 4 NOV. 1994, NETHERLANDS, vol. 229, no. 4-5, ISSN 0009-2614, pages 383 - 388, XP000574520 *
PATENT ABSTRACTS OF JAPAN vol. 005, no. 191 (P - 092) 5 December 1981 (1981-12-05) *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 103 (P - 562) 2 April 1987 (1987-04-02) *

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US8629346B2 (en) 2002-10-03 2014-01-14 Fujikura Ltd. Electrode substrate, photoelectric conversion element, conductive glass substrate and production method thereof, and pigment sensitizing solar cell
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US10056196B2 (en) 2008-04-28 2018-08-21 Fujikura Ltd. Photoelectric conversion element module
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AU4936696A (en) 1996-10-08
CH693476A5 (de) 2003-08-15
DE19680102D2 (de) 1998-03-19
DE19680102B4 (de) 2007-04-12

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