WO1996029716A1 - Procede d'application d'un certain volume de sensibilisateur sur une surface - Google Patents

Procede d'application d'un certain volume de sensibilisateur sur une surface Download PDF

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Publication number
WO1996029716A1
WO1996029716A1 PCT/CH1996/000107 CH9600107W WO9629716A1 WO 1996029716 A1 WO1996029716 A1 WO 1996029716A1 CH 9600107 W CH9600107 W CH 9600107W WO 9629716 A1 WO9629716 A1 WO 9629716A1
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WO
WIPO (PCT)
Prior art keywords
module
webs
cell
solution
plates
Prior art date
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PCT/CH1996/000107
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German (de)
English (en)
Inventor
Andreas Hinsch
Marcus Wolf
Original Assignee
Ecole Polytechnique Federale De Lausanne (Epfl)
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Publication date
Application filed by Ecole Polytechnique Federale De Lausanne (Epfl) filed Critical Ecole Polytechnique Federale De Lausanne (Epfl)
Priority to DE19680150T priority Critical patent/DE19680150D2/de
Priority to AU49367/96A priority patent/AU4936796A/en
Publication of WO1996029716A1 publication Critical patent/WO1996029716A1/fr

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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
    • H01G9/2081—Serial interconnection of cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—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
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 applying a predetermined amount of a sensitizer to a surface, wherein
  • a solution containing the predetermined amount of sensitizer is uniformly distributed over the total surface to be coated and b) with a time delay - ie only after the solution has been completely distributed over the surface to be coated - is deposited.
  • the invention further relates to a method for producing a large-area sealed module using the method mentioned. Finally, it is also a question of a long-term stable module produced in this way.
  • a regenerative photoelectrochemical cell is known from EP 0 333 641 A1 or WO 91/16719, in which conductor tracks, electrodes and a chromophore are enclosed between two plates made of glass, plastic or metal.
  • the chromophore is formed as a monomolecular layer on the surface of a metal oxide semiconductor with a high inner surface.
  • the metal oxide semiconductor is e.g. B. TiO- j .
  • the chromophore is deposited on it in the immersion bath.
  • 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.
  • 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) .
  • layer formation is no longer necessary.
  • the object of the invention is to provide a method of the type mentioned at the outset, which is particularly suitable for producing photoelectrochemical modules with a plurality of cells (PEC cells).
  • the solution according to the invention is defined by the features of claim 1.
  • the surface to be coated is designed as a nanoporous layer in order to achieve a targeted deposition by adsorption.
  • the sensitizer is prepared so that it is contained in the solution in the form of stabilized colloids.
  • the deposit takes place with a time delay. That is, A relevant destabilization of the colloids and adsorption of the molecules essentially only begins when the solution is distributed over the surface to be coated.
  • the main idea of the invention is that a time-delayed adsorption is made possible by creating a colloid solution.
  • the adsorbate can be transported in the solution in an amount which exceeds the saturation limit of a (real) molar solution many times over.
  • the stabilization of the colloids presupposes that the solubility of the adsorbate molecules in the solvent is relatively low. The individual molecules therefore only dissolve very slowly or poorly. On the other hand, the molecules on the nanoporous layer are absorbed very quickly.
  • the time delay according to the invention thus means that the time that is needed to complete the colloidal solution.
  • the time delay can be adjusted by the solubility of the adsorbate molecules in the solvent and by additional stabilization of the colloids.
  • the dynamic equilibrium between the sensitizer adsorbed on the large internal surface of the layer and the sensitizer (in an adjustable amount) in molecular solution is strongly on the deposit side. In principle, this leads to a time-controllable and ideally complete filtering out of the sensitizer from the solution.
  • the transport process according to the invention is controlled by the choice of the solvent, the choice of the coadsorbates and the adhesive groups of the sensitizer.
  • the aim should be to have a sufficiently high amount of the sensitizer in the form of stabilized colloids in a solvent in which the sensitizer is as difficult to dissolve in molecular form.
  • the surface to be coated is formed by a nanoporous layer. It is a z. B. layer formed from nanoparticles with a very high inner surface.
  • the factor of the effective geometric surface area is typically over 100, preferably 500 and more (e.g. 1000).
  • the colloids are preferably stabilized in such a way that the adsorption of the adsorbate can be initiated or accelerated in a targeted manner by irradiation of destabilizing energy onto the distributed solution or application of a voltage.
  • a voltage e.g., a voltage
  • light, heat, ultrasound or the like is used. used.
  • the adsorbate is advantageously stabilized or coadsorbated. microencapsulated.
  • the adsorbate molecules then dissolve even more slowly.
  • the idea according to the invention can be applied particularly advantageously to the production of modules with PEC cells, in which layers sensitive to atmospheric influences must be sealed inside a cell.
  • such a cell is sealed prior to the application of the adsorbate, a solution containing the adsorbate in the form of stabilized colloids is introduced into the cell through a purpose-specific filler opening, after which the time-delayed adsorption takes place or is effected.
  • adsorption should essentially only start when the solution is completely distributed in the cell.
  • the module which is sealed over a large area, consists of two thermally sealed plates serving as module walls with suitably attached electrode layers.
  • a module interior at least one cell is formed with two flat, opposite electrode layers and thus defining a cell volume.
  • a reservoir volume is formed in the module (e.g. by etching the plates) which is at least as large as the sum of the existing cell volumes.
  • a solution is filled into this, which contains the adsorbate in the form of stabilized colloids. From there, the solution is distributed over the electrode layers to be covered before the adsorption is effected with a time delay.
  • the reservoir volume is designed so that the solution can be distributed evenly as quickly as possible over the surfaces to be coated. It is not imperative that the reservoir volume be made available by a coherent area within the module. Two or more such module interiors are also conceivable, which can be filled in succession or simultaneously. Drainage channels are preferably provided which run through the interior of the module (for example at regular intervals). The drainage channels can be considered as part of the reservoir volume.
  • They preferably have a cross section which is larger than that of a cell volume (in order to be able to perform the reservoir function). Since they reduce the electrochemically activatable area in the module, they are made as small as possible.
  • a cross section of 0.5 mm x 0.5 mm or less should generally suffice.
  • the drainage channels are preferably arranged in a comb-like manner and connected at the end via at least one connecting channel (which is also assigned to the reservoir volume).
  • the volume of the connecting channel should be large enough to be able to (temporarily) accommodate the entire amount of solution.
  • the solution can be poured from the connection channel into all drainage channels at the same time (e.g. by moving the module from a first position, in which the colloidal solution is only in the connection channel, to a second position, in which the Solution can move into the drainage channels and the cell volume).
  • the arrangement of the drainage channels (and of course the entire reservoir volume) is matched to the cell-like division of the module. It goes without saying that the individual cells should be connected as far as possible within the module. As a rule, only two lines are led outside (power supply and route lines).
  • the uniform distribution of the solution and the adsorption are separated as far as possible in time.
  • the available solution volume preferably contains only about as large an amount of adsorbate as can be applied to the surface.
  • a PEC cell typically has a layered cell interior with a thickness of e.g. B. less than 200 microns.
  • a thickness e.g. B. less than 200 microns.
  • the time delay can best be controlled when targeted destabilization energy has to be radiated in, ie. H. if the colloids are stabilized in a suitable manner or are microencapsulated.
  • the solvent of the colloidal solution is also the electrolyte required in the cell.
  • this idea can also be applied to other cells, e.g. B. with electrochromic, apply.
  • the electrolyte then takes the place of e.g. B. another liquid that is required anyway in the functional cell.
  • 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.
  • reservoir areas can be provided in the cell, from which the colloids become nanoporous Diffuse layer.
  • the attached loading areas can ensure the complete loading of the nanoporous layer despite the smallness of the chamber volumes.
  • the reservoir regions can be pumped out again after a certain time and filled with a chemically inert filler.
  • the method according to the invention makes it possible to produce cells in which the cell walls are thermally sealed by a material whose sealing temperature is above the decomposition temperature of the non-heat-resistant adsorbate (eg sensitizer). This is achieved in that the cell is subjected to a thermal sealing at a temperature above a decomposition temperature of the substance mentioned in the absence of the non-heat-resistant adsorbate and that the substance is then passed through at least one suitably designed filling opening into the sealed cell is pumped in and specifically deposited.
  • a material whose sealing temperature is above the decomposition temperature of the non-heat-resistant adsorbate eg sensitizer
  • 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 processes.
  • the adsorbate for example a sensitizer, an electrochromic substance, etc.
  • the adsorbate is only filled in after the module has been sealed / encapsulated.
  • 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 method is particularly intended for the production of flat modules.
  • two plates serving as module walls are then connected at a short distance to form a layered module interior.
  • the thickness of the module is therefore much smaller than its transverse dimensions.
  • the method is typically used on 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 at a distance of less than 100 ⁇ m by webs made of thermally sealable material. Panels made of glass which are connected by webs based on glass solder are particularly preferred.
  • the sealing temperature is well above 350 ° C.
  • a type of welding of the plates (not necessarily made of glass) can also be carried out. When welding z. B. locally melted the plate material by laser radiation.
  • the thermal sealing is typically carried out in the temperature-stabilized oven. Mechanical pressure can also be used to join the panels.
  • the sealing takes place at a temperature in the range or above the transformation temperature of the glass (for example in the range from 500-750 ° C., preferably 600-650 ° C.). If, for example, the transformation temperature is 550-600 ° C, then the thermal sealing can take place at 600-700 ° C. This allows two individual plates to be connected at a precise distance from one another, even if they originally had unevenness were. Due to the small distances, a capillary force comes into effect, which the plates in a uniform distance of z. B. brings 20 microns. In the area of the transformation temperature, it is also possible to specifically shape or bend the plates. This is interesting for automotive and architectural applications (spherical, cylindrical or arbitrarily curved modules).
  • the glass soldering technique is the adhesive process based on organic or inorganic polymerizations or organic-inorganic copolymerizations with regard to long superior time 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 during the sensitization or activation.
  • the purity of the small solution volumes to be filled into the modules can also be (measured as a percentage) 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 prevents the readsorption of water vapor and other possibly harmful gases or aerosols in the highly porous semiconductor layer (carrier layer).
  • 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 characterized by the thermal outgassing or elimination of water and hydroxide groups Sealing completely water-free. 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).
  • a plurality of webs are preferably attached in order to divide the interior of the module into chambers (cells).
  • the webs increase the 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 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 using a screen printing process (or any printing technique) and (for example together with electrodes and carrier layers applied in the same way) can be sintered before the thermal sealing.
  • 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 such as B 2 0 ⁇ , PbO, Al 2 0 3 , Ce0 2 , ZrO SnO. ,, Si0 2 VO ,, ZnO, Sb., 0-., i0 2 and Ir ⁇ O-, in the form of small particles ⁇ 1 ⁇ m with volume fractions ⁇ 30%.
  • the interface properties and the Affect adhesion 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 n, 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. by a continuous flame hydrolysis process (continuous flame 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 Stegguer cut and should not exceed 50 ⁇ m. It is clear that the fillers must be thermally resistant.
  • glass solders such. B. pigments of mica, titanium dioxide, zirconium dioxide, silicon dioxide, graphite, carbon black, fluorine- or antimony-doped tin oxide, metal (z. B. Titan, aluminum) and titanium nitride in question.
  • 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 webs are provided with light-scattering filler particles. These particles can also be conductive as described above ben.
  • the light striking the webs is coupled into the adjacent photoactive region 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 coefficient of expansion which is somewhat 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 (for example made of fluorine-doped tin oxide) over the entire surface prior to the application of the conductor tracks, electrodes and webs.
  • a transparent conductive layer for example made of fluorine-doped tin oxide
  • 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 low contact contact resistances formed in this way may be due to an and mutual contact 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; Facilitation of 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 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 corresponds to at least a factor of 100, in particular a factor of 500 and more.
  • 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.
  • the drainage channels mentioned above facilitate pumping and distribution in the layered module interior. 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.
  • 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 (e.g. 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 elec- Trode coatings can be applied using screen or other printing processes. This is followed by consolidation by thermal sintering at z. B. 300-550 ° C. If the glass solder is only applied after sintering, the sintering can take place even at temperatures above 550 ° C.
  • a particularly preferred embodiment is characterized in that the electrolyte to be introduced into the module anyway is selected as the solvent. 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".
  • 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 ratio of reservoir volume to sensitizer concentration and module chamber length is expediently chosen so that the electrolyte solution is as free of sensitizer as possible after the loading process has ended.
  • 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.
  • the amount of electrolyte is preferably dimensioned such that the electrolyte can completely penetrate into the cell volume (which are defined by the electrode surfaces lying opposite one another) by capillary force.
  • the reservoir volume (specifically the cross connection) can later be passivated with an inert filling of the type described above. In this way, undesired current flows between the chambers or cells can be prevented (prevention of the separation of the electrolyte).
  • the passive influx of the sensitizer solution caused by the capillary forces in the module chambers results in rapid adsorption on only a 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 instantaneous adsorption of the sensitizer (or electrochromically activatable substance).
  • the chemisorption of the sensitizer is made possible by slow diffusion, targeted irradiation of destabilizing energy or application of an electrical voltage.
  • 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 in a single step ("discontinuous") can be activated.
  • the circuitry structure and the geometric arrangement can be carried out in a manner known per se. If the module is divided by bars into a regularly arranged two-dimensional arrangement of chambers, then it is advantageous to choose a combination of Z and P connections.
  • 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; 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 A-A according to FIG. 7;
  • FIG. 9 shows a schematic perspective illustration of section B-B 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 chip or physisorption 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 amount of dye per 2 of a nanoporous layer is first determined with a given layer thickness.
  • 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
  • the maximum permissible particle diameter It is one tenth to one hundredth of the smallest transverse dimension of the chamber volume (ie 1/10 to 1/100 of the thickness of the layered cell interior). From the molecular weight and the density of the dye and from the particle radius, the necessary number of particles and from this calculate the free particle surface.
  • 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.
  • Particle diameter approx. 100 nm - surfactant: alkylacarboxylic acids, M 100-400g / mol 30-50g / l
  • Redox mediator 1-hexyl-3-methylimidazolium iodide 200g / l iodine 13g / l
  • 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 (i.e. corresponding to the chambers) manner into electrically insulated subregions.
  • each web has a central conductive region 17.2 and two insulating regions 17.1 and 17.3 covering it.
  • 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 part of the web, which has a relatively high conductivity due to suitable filler particles. Instead of specifically increasing the conductivity in the central area 1 * 7.2, it can be lowered in the outer areas 17.1 and 17.3 with a sufficiently conductive web material (e.g. by mica).
  • a sufficiently conductive web material e.g. by 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.
  • niobium oxide, tin oxide, barium titanate, tungsten oxide etc. or doping with zirconium dioxide, aluminum oxide, silicon oxide are possible as layer material. The same effects can be achieved with substrates whose surfaces have been modified with the oxides mentioned.
  • 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-insensitive filler (corrosion resistance against the electrolyte ').
  • 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 in front through the drainage channels 7.1, ..., 8.3 guaranteed.
  • 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.
  • 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.
  • the TCO layers 3, 4 are again subdivided in the desired manner (ie in accordance with the division and geometry of the individual chambers).
  • 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 flatness 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 inorganic adhesion promoters 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 diagram 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 single-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 with a Ti0 2 _ layer 43.1,. , , , 43.3 (on the TCO layer 39), a spacing layer 44.1, ..., 44.3 and a counter electrode layer 45.1, ..., 45.3 arranged thereon.
  • 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.
  • the 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). 5, the current-carrying conductor tracks 41.1, 41.2, 41.3 are alternately attached to the glass plates 38 and 37. It is also conceivable that each web (corresponding to the P circuit according to FIG. 4) is equipped on both sides with a conductor track. However, 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 chambers 53.1, ..., 53.3, likewise formed by the webs 51.1, ..., 51.3, are each equipped with a photoelectrode layer 55.1, ..., 55.3 and a counter-electrode coating 54.1, ..., 54.3.
  • 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,
  • 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. He passes under the web 51.2 into the chamber 53.1 and changes here again the page. In contrast to the Z connection, the webs 51.1,..., 51.3 in the W connection are completely insulating. The current does not change the side between the chambers (ie 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 is (as can be seen from FIG. 9) in the lower one Glass plate 64 provided. 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 located on the upper glass plate 65 (i.e. 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 in the same way, the drainage channels 62.2 and 63.1 are analogous to the drainage channels 62.1 and 61.2 arranged.
  • 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 B-B 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.
  • FIG. 9 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 or. 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.
  • the subdivision described prevents cross currents within a strip-shaped cell (which can occur, for example, when the module is partially illuminated or overshadowed).
  • 10 shows a module with a Z-connection.
  • a multiplicity of functionally identical, strip-shaped chambers 69.1, 69.2, 69.3 form the module interior. 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. There is one in the webs 71.1, 71.2 Z connection 72.1, 72.2 housed (see, 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 contains the sensitizer in colloid-stabilized form.
  • the solution passes 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 the colloidal solution to be quickly distributed in all chambers 69.1, ....
  • the aim is that the nanoporous layers in chambers 69.1, ... are completely covered with the solution before the colloidally dispersed dye particles adsorb can be.
  • it may be necessary to destabilize the Colloidal energy eg in the form of light
  • the adsorption is initiated in a targeted manner.
  • the reservoir areas 75.1,..., 76.1 can supply dye particles (via diffusion) as long as the nanoporous layer is not "saturated".
  • the filling and distributing can proceed in such a way that initially only the connecting channel 73 is filled. Then the module is tilted (turned upside down) so that the solution can flow into all drainage channels 77.1, 77.2, ... at the same time, in order to pull into the actual cells from there (due to the capillary forces).
  • 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 described embodiments can be modified in different ways.
  • the invention fertilizer is not restricted to a specific type of connection.
  • the material specifications are also not to be interpreted as limiting 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 (i.e. large-scale) production of plate-shaped modules.

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Abstract

L'adsorbat à appliquer sur une couche dont la porosité est exprimée en nanomètres, est réparti uniformément sur l'ensemble de la surface à recouvrir dans une solution contenant l'adsorbat sous forme de colloïde stabilisé. Le volume de solution réparti uniformément contient principalement le volume prédéfini d'adsorbat à appliquer. Dès que la solution colloïdale a été répartie uniformément, l'adsorbat (déposé le cas échéant par rayonnement d'énergie de destabilisation) peut être appliqué de manière ciblée sur la surface à recouvrir. La temporisation peut être ajustée par micro-encapsulation des colloïdes et par sélection d'un solvant à faible pouvoir dissolvant. Ce procédé s'utilise dans la production de cellules photoélectrochimique thermosoudées.
PCT/CH1996/000107 1995-03-23 1996-03-21 Procede d'application d'un certain volume de sensibilisateur sur une surface WO1996029716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19680150T DE19680150D2 (de) 1995-03-23 1996-03-21 Verfahren zum Aufbringen einer vorgegebenen Menge eines Sensibilisators einf eine Oberfläche
AU49367/96A AU4936796A (en) 1995-03-23 1996-03-21 Process for applying a predetermined quantity of a sensitiserto a surface

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CH83395 1995-03-23
CH833/95-1 1995-03-23

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WO1996029716A1 true WO1996029716A1 (fr) 1996-09-26

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EP0934819A1 (fr) * 1997-08-27 1999-08-11 Kabushiki Kaisha Toyota Chuo Kenkyusho Objet enrobe et procede de fabrication de cet objet
WO2000062315A1 (fr) 1999-04-09 2000-10-19 Sustainable Technologies International Pty Ltd Procedes de mise en place de connexions isolantes et electriques dans des dispositifs photoelectrochimiques a regeneration comportant une ou plusieurs cellules
EP1164603A2 (fr) * 2000-06-15 2001-12-19 Fuji Photo Film Co., Ltd. Cellule solaire sensibilisé par un colorant
NL1020748C2 (nl) * 2002-06-04 2003-12-08 Stichting Energie Werkwijze en inrichting voor het kleuren van een laag van een nanokristallijn materiaal.
WO2005096391A2 (fr) * 2004-03-31 2005-10-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Module de cellule solaire photo-electrochimique
EP2043191A1 (fr) * 2006-07-06 2009-04-01 Sharp Kabushiki Kaisha Module de cellule solaire sensible aux colorants et procédé de fabrication correspondant
DE102008030398B4 (de) * 2007-06-29 2010-11-18 Hitachi, Ltd. Farbstoffsensibilisierte Solarzelle
EP2221842A3 (fr) * 2009-02-06 2010-12-15 University Of Wales, Bangor Cellules solaires sensibilisées aux colorants
WO2011154473A1 (fr) * 2010-06-09 2011-12-15 Bangor University Cellules solaires à colorants multiples
EP2337041A3 (fr) * 2009-12-18 2012-10-31 LG Display Co., Ltd. Module de cellules solaires sensibilisées aux colorants et son procédé de fabrication
DE102013216848A1 (de) 2013-08-23 2015-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Langzeitstabile, aus Lösungen abscheidbare photovoltaische Elemente und in-situ-Verfahren zu deren Herstellung
EP2159869A4 (fr) * 2007-06-06 2017-05-10 Fujikura, Ltd. Module de batterie solaire sensibilisée par un colorant et son procédé de fabrication
EP2252448A4 (fr) * 2007-11-27 2017-05-17 3GSolar Photovoltaics Ltd. Cellules à colorant de grande surface, et leurs procédés de fabrication

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EP1192627A4 (fr) * 1999-04-09 2005-08-24 Sustainable Technologies Inter Procedes de mise en place de connexions isolantes et electriques dans des dispositifs photoelectrochimiques a regeneration comportant une ou plusieurs cellules
WO2000062315A1 (fr) 1999-04-09 2000-10-19 Sustainable Technologies International Pty Ltd Procedes de mise en place de connexions isolantes et electriques dans des dispositifs photoelectrochimiques a regeneration comportant une ou plusieurs cellules
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US7709051B2 (en) 2002-06-04 2010-05-04 Stichting Energieonderzoek Centrum Nederland Method and apparatus for dyeing a layer of nanocrystalline material
WO2003102985A1 (fr) * 2002-06-04 2003-12-11 Stichting Energieonderzoek Centrum Nederland Procede et dispositif de coloration d'une couche de materiau nanocristallin
WO2005096391A2 (fr) * 2004-03-31 2005-10-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Module de cellule solaire photo-electrochimique
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EP2043191A4 (fr) * 2006-07-06 2012-09-19 Sharp Kk Module de cellule solaire sensible aux colorants et procédé de fabrication correspondant
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DE102013216848A1 (de) 2013-08-23 2015-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Langzeitstabile, aus Lösungen abscheidbare photovoltaische Elemente und in-situ-Verfahren zu deren Herstellung
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