WO2014072307A1 - Production method for fibrous products having a photovoltaic structure - Google Patents

Production method for fibrous products having a photovoltaic structure Download PDF

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Publication number
WO2014072307A1
WO2014072307A1 PCT/EP2013/073095 EP2013073095W WO2014072307A1 WO 2014072307 A1 WO2014072307 A1 WO 2014072307A1 EP 2013073095 W EP2013073095 W EP 2013073095W WO 2014072307 A1 WO2014072307 A1 WO 2014072307A1
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WO
WIPO (PCT)
Prior art keywords
layer
photovoltaic
coating
conductive layer
fibrous
Prior art date
Application number
PCT/EP2013/073095
Other languages
French (fr)
Inventor
Giray HASAN BERK
Original Assignee
Kordsa Global Endustriyel Iplik Ve Kordbezi Sanayi Ve Ticaret Anonim Sirketi
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Publication of WO2014072307A1 publication Critical patent/WO2014072307A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H10K30/53—Photovoltaic [PV] devices in the form of fibres or tubes, e.g. photovoltaic fibres
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a production method developed for fibrous products having a photovoltaic structure.
  • Photovoltaic structures are used to generate electricity from electromagnetic radiation based on optic and electronic properties. Photovoltaics is a feature of generating electrical potential difference upon exposure to visible or other light rays. The photovoltaic technology is currently used for such devices which convert solar energy into usable power. Photovoltaic structures are among those present renewable energy sources which comprise semiconductors converting impinging solar light directly into electrical energy.
  • Photovoltaic structures are particularly used in calculators, building roofs and windows, in traffic signals, watches, in aerospace applications, satellites, and in textile products.
  • Photovoltaic structures are used in the textile sector in an integrated fashion to textile products.
  • Textile products are made of animal-based, plant-based, or synthetic fibrous products.
  • Animal-based textile products are generally made of hairs, furs, and skins of animals.
  • Plant-based textile products are made of structures such as sisals, hemps, and mats. Structures such as cotton and bamboo are also used in the textile sector.
  • Synthetic textile products are generally in the form of polymer-based compositions. Polymer-based compositions may be exemplified with polyester, polyamide, acrylic, elastane and polylactic.
  • Textile products are subjected to a weaving process in the sector and turned into ready-to-use final textile products. Fibrous textile products are brought into yarns as a result of manual or machinery processing. The yarns, in turn, are subjected to a weaving process so that fabric-like final textile products are produced.
  • Photovoltaic textile products are obtained as a result of integrating a photovoltaic structure which generates electrical energy using the sunlight to a textile product by applying the same onto a textile material like a fabric or clothing or as a result of producing a textile product in a fibrous form.
  • Photovoltaic structures are generally integrated to a textile material in the form of a patch. It is further possible to produce a photovoltaic textile material by applying a photovoltaic structure to the entire textile material processed as a fiber.
  • the fibrous textile material into which the photovoltaic structure is integrated may be plant-based, animal-based, or synthetic. Concerning the synthetic ones, photovoltaic structures are generally integrated onto a polymer-based material using polymer-based compositions. Yarn-like compositions are preferred as the fibrous textile materials. Photovoltaic structures are integrated into these textile materials. A fibrous textile material into which a photovoltaic structure is integrated is subjected to a weaving process so as to give a final textile product.
  • Photovoltaic textile materials should be more flexible than solar panels, be resistant against twisting and stronger. In other words, photovoltaic textile materials should be resistant against wearing and bending which may occur during daily use. Photovoltaic textile materials are typically used in tents, backpacks, laptops, mobile phone case, roofing materials, etc. for generating electrical energy. Photovoltaic textile materials are also used for heating, cooling and illumination purposes besides generating electrical energy.
  • photovoltaic structures When photovoltaic structures are to be integrated to fibrous textile materials, it is quite important to maintain the photovoltaic structure during the entire steps until a final textile product is obtained. Integrating photovoltaic structures onto a fibrous textile material is carried out by means of coating.
  • the photovoltaic structure is disposed on the fibrous textile material in the form of a coating layer.
  • a textile material to which a photovoltaic structure is integrated is subjected to twisting and/or weaving process or processes to form the final textile product. Considering that the fibrous textile material is also subjected to twisting and/or weaving process or processes following the coating process to give the final textile product, the coating layer cannot be completely protected meanwhile.
  • the fact that exfoliation occurs in the coating when a twisting process is applied to the fibrous textile material to which a coating is applied results in losses in the coating and therefore the efficiency of the coating process is lowered. For this reason, the coating integrity of the photovoltaic structure should be protected following the twisting and/or weaving process or processes in obtaining the final textile product.
  • the thickness of the coating is another important parameter in fibrous textile materials to which a photovoltaic structure is integrated.
  • the coating thickness is important in terms of maximum light absorption and maximum charge collection. For this reason, the coating thickness should be quite low considering the brittleness thereof as well.
  • Photovoltaic structures are generally classified as silicon-based devices, photochemicals and organic structures. Although particularly the silicon-based devices have many application fields, some difficulties are encountered based on their production techniques, material costs, and their rigidity. In contrast, organic photovoltaic structures are quite advantageous than conventional silicon-based structures based on their flexible structures, high light transmittance, and low costs. Converting sunlight directly into electrical energy in photovoltaic structures is based to some extent on the mechanism of electric field generation. When photovoltaic devices are excited with light, a charge difference takes place due to the electronegativity difference between the electrical layers and thus an electrical potential is produced between these layers. The most effective method for generating a substantial electric field is to juxtapose two materials (layers) having a proper conductivity so that an energy level is produced.
  • the proper conductivity property is determined in accordance with the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) with respect to the distribution of molecular quantum energy states.
  • the interface of these two materials (layers), in turn, is known as the photoactive heterojunction.
  • a Fermi energy near the LUMO energy level indicates that electrons are the predominant carrier.
  • positive charges act as the predominant carrier.
  • P-n (p-type:n-type) hetero junctions exhibit diode rectification.
  • the basic mechanism of "P-n hetero junctions" are based on the interface between p-type (donor) and n-type (acceptor) materials.
  • Photovoltaic structures can be integrated to a final textile product in the form of a patch, or it can be integrated on a fibrous textile material by means of coating.
  • a fibrous textile material into which a photovoltaic structure is integrated is subjected to twisting and/or weaving process or processes so as to give the final textile product. Protecting the integrity of the photovoltaic structure during these process steps is important. However, the photovoltaic structure coated onto a fibrous textile material becomes damaged particularly during the twisting process and the coating may exfoliate.
  • the patent application US20030042846A1 according to the prior art , which aims to solve the present problem, relates to organic photosensitive optoelectronic structures.
  • groups of layers are connected to each other in series using repeating coating layers for increasing the efficiency.
  • Another patent application US20060013549A1 relates to organic optoelectronic structures having a fiber structure.
  • the fiber has a conductive core including an electrode, and an organic layer is provided which is connected to this electrode.
  • the organic layer is electrically connected to a second electrode system.
  • the patent application US5331 183A relates to heterojunction diodes suitable for use in photovoltaic systems. Brief Description of Invention
  • a production method developed according to the present invention for fibrous textile materials having a photovoltaic structure comprises the steps of applying a twisting process to the fibrous material, forming a substrate by subjecting the fibrous material from the twisting process to a preliminary surface treatment, coating the substrate with a photovoltaic coating layer, encapsulating, and winding the same.
  • Said photovoltaic coating layer comprises in succession at least one conductive layer, at least one continuous conductive layer, at least one photoactive heterojunction layer, at least one continuous conductive layer, and at least one metal layer.
  • the object of the present invention is to develop a production method for fibrous materials having a photovoltaic structure.
  • Another object of the present invention is to develop a production method for fibrous materials having a photovoltaic structure, wherein the exfoliation of the coating layer is prevented and the coating layer is retained on the surface in an ideal manner.
  • a further object of the present invention is to develop a simple, inexpensive, and efficient production method for fibrous materials having a photovoltaic structure. Description of Figures
  • a production method developed according to the present invention for a fibrous textile material having a photovoltaic structure is illustrated in the accompanying figures briefly described below.
  • Figure 1 is a representative illustration of a twisted fibrous textile material which can be suitably coated.
  • Figure 2 is a representative flow diagram of the production method.
  • Figure 3 is a representative illustration of the coating layers.
  • Photovoltaic structures can produce electrical energy using the sunlight. Generating electrical energy from sunlight is advantageous in that the sun is a clean and renewable energy source as compared to other energy sources.
  • Photovoltaic structures can be integrated to textile products. Photovoltaic textile products are particularly advantageous in terms of generating electrical energy when utility sources are not nearby.
  • Photovoltaic structures can be applied to final textile products in the form of patches, or they can be integrated onto fibrous textile materials. Fibrous textile materials can be obtained from animal, plant, or synthetic sources. Concerning the synthetic ones, photovoltaic structures are generally integrated to polymer-based fibrous textile materials. The photovoltaic structure is integrated by means of coating the surface of the fibrous textile material in the form of coating layers to provide a suitable electron flow.
  • Integrating the photovoltaic structure to a final textile product (e.g. a fabric) in the form of a patch results in drawbacks in terms of use, energy utilization, flexibility, and cleaning.
  • Concerning a fibrous textile material the integrated photovoltaic structure may be damaged during the twisting step and/or the weaving step for producing the final textile product and losses may occur in the coating.
  • a production method is developed with the present invention for a fibrous textile material having a photovoltaic structure suitable for a textile production process in order to obtain a fibrous textile product having an effective photovoltaic structure.
  • a representative flow diagram of the production method according to the present invention for a fibrous textile material having a photovoltaic structure is given in Figure 2.
  • FIG. 1 a representative illustration of a twisted fibrous material (L) suitable for coating is given in Figure 1.
  • the fibrous material (L) is subjected to a twisting process (1 ) suitable for textile production and a photovoltaic coating (3) process is carried out in order to integrate a photovoltaic structure thereto.
  • the production method developed according to the present invention comprises the steps of carrying out a twisting process (1 ), a preparatory surface treatment (2), a photovoltaic coating (3), an encapsulation process (4), and a winding process (5).
  • the fibrous material (L) is first subjected to the twisting process (1 ) during the entire textile production. After the fibrous material (L) is subjected to the twisting process (1 ), it is subjected to preliminary surface treatment (2) using chemicals which enhance surface retention. Using this process, the surface is made suitable for coating with photovoltaic coating (3) layers and a substrate (100) is formed providing a maximum retention capability for the photovoltaic coating (3) layers on the surface.
  • a conductive layer (1 10) coated with a chemical providing electrical conductivity on a suitable HOMO-LUMO [highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)] level is disposed on the substrate (100).
  • a continuous conductive layer (120) is coated onto the conductive layer (1 10) to maintain electrical conductivity. Said continuous conductive layer (120) protects the coating layers disposed on its lower and upper surfaces and increases the efficiency of the layer.
  • a photoactive heterojunction layer (130) comprising a material layer which activates with light and is composed of two polymers, one electron accepting and the other electron donating.
  • the encapsulation process (4) is carried out on the fibrous material (L), which is previously subjected to the twisting process (1 ) and coated with photovoltaic coating (3) layers in order to increase the efficiency of the layers.
  • the fibrous material (L) subjected to said processes is finally subjected to the winding process (5) according to the requirements of textile production.
  • the photovoltaic coating (3) layer representatively illustrated in Figure 3 comprises in succession a substrate material (100), a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140). Converting sunlight directly into electrical energy in photovoltaic structures is based to some extent on the mechanism of electric field generation.
  • the photovoltaic coating (3) layer used in the production method according to the present invention for fibrous textile materials having photovoltaic structures comprises a conductive layer (1 10) providing a suitable HOMO-LUMO level electrical conductivity onto the substrate (100).
  • Said conductive layer (1 10) is a cathode layer or an anode layer.
  • the continuous conductive layer (120) functions as an electron transmission layer providing the transmittance of electrons due to high electron variability.
  • the continuous conductive layer (120) functions as a positive charge layer (hole transport layer).
  • a photoactive heterojunction layer (130) composed of two polymers, one electron accepting and the other electron donating, is disposed between the conductive layer (1 10) and the metal layer (140) in addition to the continuous conductive layer (120).
  • an electric current is applied to the electrically connected conductive layer (1 10) and the metal layer (140) in the photovoltaic structure, positive and negative charges are transferred between the layers and migrated to charged layers so as to produce an excitation.
  • coating combinations can be used which are composed of various chemicals capable to increase the layer efficiency of the photovoltaic coating (3) layers illustrated in Figure 3.
  • These chemicals can preferably be ITO (indium tin oxide), 3,4- polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PPS), silver, graphene, and carbon nanotube for the conductive layer (1 10), and preferably PEDOT:PPS, V 2 0 5 (vanadium pentoxide), Mo0 3 (molybdenum trioxide), LiF (lithium fluoride), calcium, ZnO (zinc oxide), Ti0 2 (titanium dioxide), graphene and carbon nanotub for the continuous conductive layer (120).
  • ITO indium tin oxide
  • PEDOT:PPS 3,4- polyethylenedioxythiophene:polystyrenesulfonate
  • silver graphene
  • carbon nanotube for the conductive layer (1 10)
  • PEDOT:PPS preferably PEDOT:PPS, V 2 0 5 (vanadium pentoxide), Mo0 3 (molybdenum trioxide), LiF (lithium flu
  • Said chemicals can preferably be poly((4,8-bis(2- ethylhexyloxy)benzo(1 ,2-b:4,5b')dithiophene-2,6-diyl)(2-((n-octyloxy)carbonyl)(3- fluoro)thieno(3,4-b)thiophenediyl)) (PTB4), phenyl-C 6 rbutyric acid methyl ester (PCBM), poly(3-hexylthiophene) (P3HT), poly(4,8-bis-alkyloxybenzo(1 ,2-b:4,5-b')dithiophene-2,6- diyl-alt-(alkylthieno(3,4-b)thiophene-2-(2-ethyl-1 -hexanone)-2,6-diyl) (PBDTTT-C), ICBA (indene-C 6 o double addition product), C 6 o fullerene,
  • At least one of these chemicals given for the photoactive heterojunction layer (130) is present as an electron acceptor and at least another thereof as an electron donor in the form of a mixture.
  • the chemicals can preferably be aluminium, silver, and gold.
  • the layers used as the photovoltaic coating (3) layer are applied onto the substrate (100) using various known techniques such as vacuum thermal annealing, dip coating, rotary coating, vapor phase deposition etc..
  • the encapsulation process (4) to be applied to the textile material with a fibrous structure (L), which is previously subjected to the twisting process (1 ) and coated with photovoltaic coating (3) layers, in turn, is carried out by a lamination technique.
  • a winding operation (5) is carried out with the help of a winder in accordance with textile production processes.
  • the coating thickness in the coating process carried out with photovoltaic coating (3) layers on the fibrous structure (L) previously subjected to the twisting process (1 ) also influences the function of the system and the efficiency of the coating. Selecting a proper coating thickness influences the factors such as light absorption and flexibility as well. Therefore the coating thickness should be made optimum.
  • the thickness of the photovoltaic coating (3) layers to be applied onto the substrate (100) is 1 -1000 nanometers (nm).
  • the production method developed according to the present invention is suitable for textile materials with a fibrous structure (L).
  • the fibrous structure (L) preferably comprises a polymer-based material.
  • Said polymer-based material can have polyamide or polyester surfaces.
  • the texture of the textile material having a fibrous structure (L) can have a multifilament form or a monofilament form.
  • the production method developed according to the present invention is suitable for textile materials with a fibrous structure (L) having photovoltaic feature.
  • Said photovoltaic feature is preferably an organic photovoltaic structure.
  • the photovoltaic coating layer (3) disposed in said organic photovoltaic structure has an organic structure.
  • a fibrous structure (L) is subjected to a twisting process (1 ), and then to a preliminary surface treatment (2) using chemicals which enhance surface retention via a dip coating method.
  • a photovoltaic coating layer (3) composed of a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140).
  • the conductive layer (1 10) is a cathode layer
  • the continuous conductive layer (120) is an electron transmission layer providing electron transmission to the cathode layer.
  • the photoactive heterojunction layer (130) On the photoactive heterojunction layer (130), in turn, is disposed a positive charge layer providing the continuity of conduction between this layer and the metal layer (140). As for the metal layer (140), it is disposed as an anode layer.
  • the substrate (100) is coated with the photovoltaic coating (3) layer composed in succession of the cathode layer, electron transmission layer, photoactive heterojunction layer (130), positive charge layer, and the anode layer.
  • the photoactive heterojunction layer (130) is composed of two materials, one electron accepting and the other electron donating. First the cathode layer is applied onto the substrate (100) by means of spray coating or dip coating, and then the electron transmission layer and the photoactive heterojunction layer (130) are applied by means of dip coating.
  • the fibrous structure (L) On said photoactive heterojunction layer (130), in turn, is applied the positive charge layer by means of spray coating or dip coating, and then the anode layer is applied by means of vacuum heat evaporation.
  • the fibrous structure (L) previously subjected to twisting (1 ) and then coated with photovoltaic coating (3) layers is then subjected to an encapsulation process (4) by means of a lamination technique.
  • the fibrous structure (L) having undergone the operations for producing the final textile product in line with textile production process is finally subjected to a winding process (5). Carrying out the twisting process (1 ) on the fibrous structure (L) prior to applying the photovoltaic coating layers (3) thereto will minimize the losses and damages which may take place during coating.
  • the fibrous structure (L) preferably comprises a polymer-based material. And said polymer-based material can have polyamide or polyester surfaces.
  • a fibrous structure (L) is subjected to a twisting process (1 ) and then to a preliminary surface treatment (2) using surface retention enhancing chemicals via a dip coating method.
  • a photovoltaic coating layer (3) composed of a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140).
  • the conductive layer (1 10) is an anode layer
  • the continuous conductive layer (120) is a positive charge transmission layer providing the transmission of positive charges to the anode layer.
  • the photoactive heterojunction layer (130) On the photoactive heterojunction layer (130), in turn, is disposed an electron transmission layer providing the continuity of conduction between this layer and the metal layer (140). As for the metal layer (140), it is disposed as a cathode layer.
  • the substrate (100) is coated with the photovoltaic coating (3) layer composed in succession of the anode layer, positive charge layer, photoactive heterojunction layer (130), electron transmission layer, and the cathode layer.
  • the photoactive heterojunction layer (130) is composed of two materials, one electron accepting and the other electron donating.
  • the anode layer is applied onto the substrate (100) by means of spray coating or dip coating, and then the positive charge layer is applied by means of spray coating or dip coating and the photoactive heterojunction layer (130) is applied by means of dip coating.
  • the photoactive heterojunction layer (130) is coated the electron transmission layer and the cathode layer by means of vacuum heat evaporation.
  • the fibrous structure (L) previously subjected to twisting (1 ) and then coated the photovoltaic coating (3) layers is then subjected to an encapsulation process (4) by means of a lamination technique.
  • the fibrous structure (L) having undergone the operations for producing the final textile product in line with textile production process is finally subjected to a winding process (5).
  • the fibrous structure (L) preferably comprises a polymer-based material.
  • said polymer-based material can have polyamide or polyester surfaces.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A production method according to the present invention for textile materials with a fibrous structure (L) having photovoltaic property comprises the steps of carrying out a twisting process (1) on the fibrous structure (L); subjecting the fibrous structure (L) having undergone the twisting process (1) to a preliminary surface treatment (2) to form a substrate (100); coating the substrate (100) with a photovoltaic coating (3) layer composed of at least one conductive layer (110), at least one continuous conductive layer (120), at least one photoactive heterojunction layer (130), at least one continuous conductive layer (120), and at least one metal layer (140); conducting an encapsulation process (4) and a winding process (5).

Description

DESCRIPTION
PRODUCTION METHOD FOR FIBROUS PRODUCTS HAVING A PHOTOVOLTAIC
STRUCTURE Field of Invention
The present invention relates to a production method developed for fibrous products having a photovoltaic structure. Prior Art
Photovoltaic structures are used to generate electricity from electromagnetic radiation based on optic and electronic properties. Photovoltaics is a feature of generating electrical potential difference upon exposure to visible or other light rays. The photovoltaic technology is currently used for such devices which convert solar energy into usable power. Photovoltaic structures are among those present renewable energy sources which comprise semiconductors converting impinging solar light directly into electrical energy.
The use of solar energy as a clean, inexhaustible, and renewable energy resource have become advantageous due to the gradual depletion of energy resources and the environmental pollution resulting from the electrical energy generation from the current resources. Photovoltaic structures are particularly used in calculators, building roofs and windows, in traffic signals, watches, in aerospace applications, satellites, and in textile products.
Photovoltaic structures are used in the textile sector in an integrated fashion to textile products. Textile products are made of animal-based, plant-based, or synthetic fibrous products. Animal-based textile products are generally made of hairs, furs, and skins of animals. Plant-based textile products, in turn, are made of structures such as sisals, hemps, and mats. Structures such as cotton and bamboo are also used in the textile sector. Synthetic textile products are generally in the form of polymer-based compositions. Polymer-based compositions may be exemplified with polyester, polyamide, acrylic, elastane and polylactic. Textile products are subjected to a weaving process in the sector and turned into ready-to-use final textile products. Fibrous textile products are brought into yarns as a result of manual or machinery processing. The yarns, in turn, are subjected to a weaving process so that fabric-like final textile products are produced.
Photovoltaic textile products are obtained as a result of integrating a photovoltaic structure which generates electrical energy using the sunlight to a textile product by applying the same onto a textile material like a fabric or clothing or as a result of producing a textile product in a fibrous form. Photovoltaic structures are generally integrated to a textile material in the form of a patch. It is further possible to produce a photovoltaic textile material by applying a photovoltaic structure to the entire textile material processed as a fiber. The fibrous textile material into which the photovoltaic structure is integrated may be plant-based, animal-based, or synthetic. Concerning the synthetic ones, photovoltaic structures are generally integrated onto a polymer-based material using polymer-based compositions. Yarn-like compositions are preferred as the fibrous textile materials. Photovoltaic structures are integrated into these textile materials. A fibrous textile material into which a photovoltaic structure is integrated is subjected to a weaving process so as to give a final textile product.
Concerning the process of applying a photovoltaic structure to a textile product in the form of a patch, exploiting the sunlight takes place only at the site where the photovoltaic structure is integrated to the textile material since the former is not integrated to the entire area of the latter. This, in turn, leads to an insufficient utilization of the solar energy. Additionally, photovoltaic structures integrated in the form of a patch cannot provide features such as flexibility or an easy cleaning. In contrast, when the photovoltaic structure is integrated to the entire area of a fibrous textile material, the sunlight is used to a substantial extent and the textile product provides high flexibility.
Generating electrical energy under the photovoltaic effect by means of clothes worn or other textile materials used is particularly very useful to provide energy to small electronic devices used by those who have to work or visit places which are far from urban electric networks. Photovoltaic textile materials should be more flexible than solar panels, be resistant against twisting and stronger. In other words, photovoltaic textile materials should be resistant against wearing and bending which may occur during daily use. Photovoltaic textile materials are typically used in tents, backpacks, laptops, mobile phone case, roofing materials, etc. for generating electrical energy. Photovoltaic textile materials are also used for heating, cooling and illumination purposes besides generating electrical energy.
When photovoltaic structures are to be integrated to fibrous textile materials, it is quite important to maintain the photovoltaic structure during the entire steps until a final textile product is obtained. Integrating photovoltaic structures onto a fibrous textile material is carried out by means of coating. The photovoltaic structure is disposed on the fibrous textile material in the form of a coating layer. A textile material to which a photovoltaic structure is integrated is subjected to twisting and/or weaving process or processes to form the final textile product. Considering that the fibrous textile material is also subjected to twisting and/or weaving process or processes following the coating process to give the final textile product, the coating layer cannot be completely protected meanwhile. The fact that exfoliation occurs in the coating when a twisting process is applied to the fibrous textile material to which a coating is applied results in losses in the coating and therefore the efficiency of the coating process is lowered. For this reason, the coating integrity of the photovoltaic structure should be protected following the twisting and/or weaving process or processes in obtaining the final textile product. The thickness of the coating is another important parameter in fibrous textile materials to which a photovoltaic structure is integrated. The coating thickness is important in terms of maximum light absorption and maximum charge collection. For this reason, the coating thickness should be quite low considering the brittleness thereof as well.
Photovoltaic structures are generally classified as silicon-based devices, photochemicals and organic structures. Although particularly the silicon-based devices have many application fields, some difficulties are encountered based on their production techniques, material costs, and their rigidity. In contrast, organic photovoltaic structures are quite advantageous than conventional silicon-based structures based on their flexible structures, high light transmittance, and low costs. Converting sunlight directly into electrical energy in photovoltaic structures is based to some extent on the mechanism of electric field generation. When photovoltaic devices are excited with light, a charge difference takes place due to the electronegativity difference between the electrical layers and thus an electrical potential is produced between these layers. The most effective method for generating a substantial electric field is to juxtapose two materials (layers) having a proper conductivity so that an energy level is produced. The proper conductivity property, in turn, is determined in accordance with the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) with respect to the distribution of molecular quantum energy states. The interface of these two materials (layers), in turn, is known as the photoactive heterojunction. A Fermi energy near the LUMO energy level indicates that electrons are the predominant carrier. In contrast, when the Fermi energy is near the HOMO energy level, positive charges act as the predominant carrier. "P-n (p-type:n-type) hetero junctions" exhibit diode rectification. The basic mechanism of "P-n hetero junctions" are based on the interface between p-type (donor) and n-type (acceptor) materials. This formation actually originates from the different electronegative properties of two materials. When electrons and protons emit light in the vicinity of the junction, the difference in the electronegativity serve to separate the charging. Photovoltaic structures can be integrated to a final textile product in the form of a patch, or it can be integrated on a fibrous textile material by means of coating. A fibrous textile material into which a photovoltaic structure is integrated is subjected to twisting and/or weaving process or processes so as to give the final textile product. Protecting the integrity of the photovoltaic structure during these process steps is important. However, the photovoltaic structure coated onto a fibrous textile material becomes damaged particularly during the twisting process and the coating may exfoliate.
The patent application US20030042846A1 according to the prior art , which aims to solve the present problem, relates to organic photosensitive optoelectronic structures. In said patent application, groups of layers are connected to each other in series using repeating coating layers for increasing the efficiency. Another patent application US20060013549A1 , in turn, relates to organic optoelectronic structures having a fiber structure. In said patent application, the fiber has a conductive core including an electrode, and an organic layer is provided which is connected to this electrode. The organic layer, in turn, is electrically connected to a second electrode system. The patent application US5331 183A relates to heterojunction diodes suitable for use in photovoltaic systems. Brief Description of Invention
A production method developed according to the present invention for fibrous textile materials having a photovoltaic structure comprises the steps of applying a twisting process to the fibrous material, forming a substrate by subjecting the fibrous material from the twisting process to a preliminary surface treatment, coating the substrate with a photovoltaic coating layer, encapsulating, and winding the same. Said photovoltaic coating layer comprises in succession at least one conductive layer, at least one continuous conductive layer, at least one photoactive heterojunction layer, at least one continuous conductive layer, and at least one metal layer.
In the production method developed according to the present invention, carrying out the twisting process prior to the step of integrating the photovoltaic coating layer to the textile material with a fiber structure protects the photovoltaic coating layer against damages and against the exfoliation of the coating layer and minimizes the lowering of the efficiency to be obtained from the coating. Photovoltaic coating, encapsulation, and winding steps are carried out in succession on the fibrous textile material to which a twisting process is applied for producing a textile product. Thus, the fibrous textile material having a photovoltaic structure is made ready for producing a final textile product.
Object of Invention
The object of the present invention is to develop a production method for fibrous materials having a photovoltaic structure.
Another object of the present invention is to develop a production method for fibrous materials having a photovoltaic structure, wherein the exfoliation of the coating layer is prevented and the coating layer is retained on the surface in an ideal manner. A further object of the present invention is to develop a simple, inexpensive, and efficient production method for fibrous materials having a photovoltaic structure. Description of Figures
A production method developed according to the present invention for a fibrous textile material having a photovoltaic structure is illustrated in the accompanying figures briefly described below.
Figure 1 is a representative illustration of a twisted fibrous textile material which can be suitably coated.
Figure 2 is a representative flow diagram of the production method.
Figure 3 is a representative illustration of the coating layers.
The parts in said figures are individually referenced as following.
Fibrous structure (L)
Twisting process (1 )
Preliminary surface treatment (2)
Photovoltaic coating (3)
Encapsulation (4)
Winding (5)
Substrate (100)
Conductive layer (1 10)
Continues conductive layer (120)
Photoactive heterojunction layer (130)
Metal layer (140)
Description of Invention
Photovoltaic structures can produce electrical energy using the sunlight. Generating electrical energy from sunlight is advantageous in that the sun is a clean and renewable energy source as compared to other energy sources. Photovoltaic structures can be integrated to textile products. Photovoltaic textile products are particularly advantageous in terms of generating electrical energy when utility sources are not nearby. Photovoltaic structures can be applied to final textile products in the form of patches, or they can be integrated onto fibrous textile materials. Fibrous textile materials can be obtained from animal, plant, or synthetic sources. Concerning the synthetic ones, photovoltaic structures are generally integrated to polymer-based fibrous textile materials. The photovoltaic structure is integrated by means of coating the surface of the fibrous textile material in the form of coating layers to provide a suitable electron flow.
Integrating the photovoltaic structure to a final textile product (e.g. a fabric) in the form of a patch results in drawbacks in terms of use, energy utilization, flexibility, and cleaning. Concerning a fibrous textile material, the integrated photovoltaic structure may be damaged during the twisting step and/or the weaving step for producing the final textile product and losses may occur in the coating. For this reason, a production method is developed with the present invention for a fibrous textile material having a photovoltaic structure suitable for a textile production process in order to obtain a fibrous textile product having an effective photovoltaic structure. A representative flow diagram of the production method according to the present invention for a fibrous textile material having a photovoltaic structure is given in Figure 2. Here, a representative illustration of a twisted fibrous material (L) suitable for coating is given in Figure 1. The fibrous material (L) is subjected to a twisting process (1 ) suitable for textile production and a photovoltaic coating (3) process is carried out in order to integrate a photovoltaic structure thereto.
The production method developed according to the present invention comprises the steps of carrying out a twisting process (1 ), a preparatory surface treatment (2), a photovoltaic coating (3), an encapsulation process (4), and a winding process (5). The fibrous material (L) is first subjected to the twisting process (1 ) during the entire textile production. After the fibrous material (L) is subjected to the twisting process (1 ), it is subjected to preliminary surface treatment (2) using chemicals which enhance surface retention. Using this process, the surface is made suitable for coating with photovoltaic coating (3) layers and a substrate (100) is formed providing a maximum retention capability for the photovoltaic coating (3) layers on the surface. A conductive layer (1 10) coated with a chemical providing electrical conductivity on a suitable HOMO-LUMO [highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)] level is disposed on the substrate (100). A continuous conductive layer (120) is coated onto the conductive layer (1 10) to maintain electrical conductivity. Said continuous conductive layer (120) protects the coating layers disposed on its lower and upper surfaces and increases the efficiency of the layer. On the continuous conductive layer (120), in turn, is disposed a photoactive heterojunction layer (130) comprising a material layer which activates with light and is composed of two polymers, one electron accepting and the other electron donating. A metal layer (140), in which typically metals are used, is disposed on the continuous conductive layer (120) maintaining the electrical conductivity on the photoactive heterojunction layer (130). The encapsulation process (4) is carried out on the fibrous material (L), which is previously subjected to the twisting process (1 ) and coated with photovoltaic coating (3) layers in order to increase the efficiency of the layers. The fibrous material (L) subjected to said processes is finally subjected to the winding process (5) according to the requirements of textile production.
Carrying out a twisting operation (1 ) in the textile production process after the textile materials with a fibrous structure (L) are coated with photovoltaic coating (3) layers may damage the coating layers; therefore the fibrous structure (L) is first subjected to the twisting operation (1 ) according to the production method. Thus, the coating is protected against losses in the following production steps after the photovoltaic structures are coated. The photovoltaic coating (3) layer representatively illustrated in Figure 3 comprises in succession a substrate material (100), a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140). Converting sunlight directly into electrical energy in photovoltaic structures is based to some extent on the mechanism of electric field generation. The photovoltaic coating (3) layer used in the production method according to the present invention for fibrous textile materials having photovoltaic structures comprises a conductive layer (1 10) providing a suitable HOMO-LUMO level electrical conductivity onto the substrate (100). Said conductive layer (1 10) is a cathode layer or an anode layer. The continuous conductive layer (120) disposed on the conductive layer (1 10), in turn, provides conductive continuity between the lower and upper layers. When the conductive layer (1 10) is a cathode, the continuous conductive layer (120) functions as an electron transmission layer providing the transmittance of electrons due to high electron variability. And when the conductive layer (1 10) is anodic, the continuous conductive layer (120) functions as a positive charge layer (hole transport layer). A photoactive heterojunction layer (130) composed of two polymers, one electron accepting and the other electron donating, is disposed between the conductive layer (1 10) and the metal layer (140) in addition to the continuous conductive layer (120). When an electric current is applied to the electrically connected conductive layer (1 10) and the metal layer (140) in the photovoltaic structure, positive and negative charges are transferred between the layers and migrated to charged layers so as to produce an excitation. In order to activate the coating in the production method developed according to the present invention, coating combinations can be used which are composed of various chemicals capable to increase the layer efficiency of the photovoltaic coating (3) layers illustrated in Figure 3. These chemicals can preferably be ITO (indium tin oxide), 3,4- polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PPS), silver, graphene, and carbon nanotube for the conductive layer (1 10), and preferably PEDOT:PPS, V205 (vanadium pentoxide), Mo03 (molybdenum trioxide), LiF (lithium fluoride), calcium, ZnO (zinc oxide), Ti02 (titanium dioxide), graphene and carbon nanotub for the continuous conductive layer (120). Said chemicals can preferably be poly((4,8-bis(2- ethylhexyloxy)benzo(1 ,2-b:4,5b')dithiophene-2,6-diyl)(2-((n-octyloxy)carbonyl)(3- fluoro)thieno(3,4-b)thiophenediyl)) (PTB4), phenyl-C6rbutyric acid methyl ester (PCBM), poly(3-hexylthiophene) (P3HT), poly(4,8-bis-alkyloxybenzo(1 ,2-b:4,5-b')dithiophene-2,6- diyl-alt-(alkylthieno(3,4-b)thiophene-2-(2-ethyl-1 -hexanone)-2,6-diyl) (PBDTTT-C), ICBA (indene-C6o double addition product), C6o fullerene, DPP (diketopyrrolopyrrole) polymers for the photoactive heterojunction layer (130). At least one of these chemicals given for the photoactive heterojunction layer (130) is present as an electron acceptor and at least another thereof as an electron donor in the form of a mixture. As for the metal layer (140), the chemicals can preferably be aluminium, silver, and gold. Thus, the efficiency of the photovoltaic coating (3) layers to be applied following the twisting operation (1 ) is increased.
In the production method developed according to the present invention for textile materials with a fibrous structure (L) having photovoltaic property, the layers used as the photovoltaic coating (3) layer are applied onto the substrate (100) using various known techniques such as vacuum thermal annealing, dip coating, rotary coating, vapor phase deposition etc.. The encapsulation process (4) to be applied to the textile material with a fibrous structure (L), which is previously subjected to the twisting process (1 ) and coated with photovoltaic coating (3) layers, in turn, is carried out by a lamination technique. Then, a winding operation (5) is carried out with the help of a winder in accordance with textile production processes.
In the production method developed according to the present invention, the coating thickness in the coating process carried out with photovoltaic coating (3) layers on the fibrous structure (L) previously subjected to the twisting process (1 ) also influences the function of the system and the efficiency of the coating. Selecting a proper coating thickness influences the factors such as light absorption and flexibility as well. Therefore the coating thickness should be made optimum. In the production method developed according to the present invention, the thickness of the photovoltaic coating (3) layers to be applied onto the substrate (100) is 1 -1000 nanometers (nm).
The production method developed according to the present invention is suitable for textile materials with a fibrous structure (L). The fibrous structure (L) preferably comprises a polymer-based material. Said polymer-based material can have polyamide or polyester surfaces. The texture of the textile material having a fibrous structure (L) can have a multifilament form or a monofilament form.
The production method developed according to the present invention is suitable for textile materials with a fibrous structure (L) having photovoltaic feature. Said photovoltaic feature is preferably an organic photovoltaic structure. The photovoltaic coating layer (3) disposed in said organic photovoltaic structure has an organic structure.
In a preferred embodiment of the production method developed according to the present invention, a fibrous structure (L) is subjected to a twisting process (1 ), and then to a preliminary surface treatment (2) using chemicals which enhance surface retention via a dip coating method. On a substrate (100) formed as a result of the preliminary surface treatment (2) is coated a photovoltaic coating layer (3) composed of a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140). Here, when the conductive layer (1 10) is a cathode layer, the continuous conductive layer (120) is an electron transmission layer providing electron transmission to the cathode layer. On the photoactive heterojunction layer (130), in turn, is disposed a positive charge layer providing the continuity of conduction between this layer and the metal layer (140). As for the metal layer (140), it is disposed as an anode layer. The substrate (100) is coated with the photovoltaic coating (3) layer composed in succession of the cathode layer, electron transmission layer, photoactive heterojunction layer (130), positive charge layer, and the anode layer. The photoactive heterojunction layer (130) is composed of two materials, one electron accepting and the other electron donating. First the cathode layer is applied onto the substrate (100) by means of spray coating or dip coating, and then the electron transmission layer and the photoactive heterojunction layer (130) are applied by means of dip coating. On said photoactive heterojunction layer (130), in turn, is applied the positive charge layer by means of spray coating or dip coating, and then the anode layer is applied by means of vacuum heat evaporation. The fibrous structure (L) previously subjected to twisting (1 ) and then coated with photovoltaic coating (3) layers is then subjected to an encapsulation process (4) by means of a lamination technique. The fibrous structure (L) having undergone the operations for producing the final textile product in line with textile production process is finally subjected to a winding process (5). Carrying out the twisting process (1 ) on the fibrous structure (L) prior to applying the photovoltaic coating layers (3) thereto will minimize the losses and damages which may take place during coating. Here, the fibrous structure (L) preferably comprises a polymer-based material. And said polymer-based material can have polyamide or polyester surfaces.
In another preferred embodiment of the production method developed according to the present invention, in turn, a fibrous structure (L) is subjected to a twisting process (1 ) and then to a preliminary surface treatment (2) using surface retention enhancing chemicals via a dip coating method. On a substrate material (100) formed as a result of the preliminary surface treatment (2) is coated a photovoltaic coating layer (3) composed of a conductive layer (1 10), a continuous conductive layer (120), a photoactive heterojunction layer (130), a continuous conductive layer (120), and a metal layer (140). Here, when the conductive layer (1 10) is an anode layer, the continuous conductive layer (120) is a positive charge transmission layer providing the transmission of positive charges to the anode layer. On the photoactive heterojunction layer (130), in turn, is disposed an electron transmission layer providing the continuity of conduction between this layer and the metal layer (140). As for the metal layer (140), it is disposed as a cathode layer. The substrate (100) is coated with the photovoltaic coating (3) layer composed in succession of the anode layer, positive charge layer, photoactive heterojunction layer (130), electron transmission layer, and the cathode layer. The photoactive heterojunction layer (130) is composed of two materials, one electron accepting and the other electron donating. First the anode layer is applied onto the substrate (100) by means of spray coating or dip coating, and then the positive charge layer is applied by means of spray coating or dip coating and the photoactive heterojunction layer (130) is applied by means of dip coating. On said photoactive heterojunction layer (130), in turn, are coated the electron transmission layer and the cathode layer by means of vacuum heat evaporation. The fibrous structure (L) previously subjected to twisting (1 ) and then coated the photovoltaic coating (3) layers is then subjected to an encapsulation process (4) by means of a lamination technique. The fibrous structure (L) having undergone the operations for producing the final textile product in line with textile production process is finally subjected to a winding process (5). Carrying out the twisting process (1 ) on the fibrous structure (L) prior to applying the photovoltaic coating layers (3) thereto will minimize the losses and damages which may take place during coating. Here, the fibrous structure (L) preferably comprises a polymer-based material. And said polymer-based material can have polyamide or polyester surfaces.

Claims

1. A production method for textile materials having a fibrous structure (L) with photovoltaic property, characterized by comprising the steps of
carrying out a twisting process (1 ) on the fibrous structure (L);
subjecting the fibrous structure (L) having undergone the twisting process (1 ) to a preliminary surface treatment (2) in order to form a substrate (100); coating the substrate (100) with a photovoltaic coating (3) layer composed of at least one conductive layer (1 10), at least one continuous conductive layer (120), at least one photoactive heterojunction layer (130), at least one continuous conductive layer (120), and at least one metal layer (140);
conducting an encapsulation process (4) and a winding process (5).
2. A method according to Claim 1 , characterized in that said fibrous structure (L) comprises a polymer-based material.
3. A method according to Claim 2, characterized in that said fibrous structure (L) comprises a polyamide surface or a polyester surface.
4. A method according to Claim 1 , characterized in that said photovoltaic coating layer (3) has an organic structure.
5. A method according to Claim 1 , characterized in that said photovoltaic coating (3) layer has a thickness of 1 -1000 nm.
6. A method according to Claim 1 , characterized in that said conductive layer (1 10) is a cathode layer.
7. A method according to Claim 1 , characterized in that said conductive layer (1 10) is an anode layer.
8. A method according to Claim 1 , characterized in that said continuous conductive layer (120) is an electron transmission layer.
9. A method according to Claim 1 , characterized in that said continuous conductive layer (120) is a positive charge layer.
10. A method according to Claim 1 , characterized in that said metal layer (140) is a cathode layer.
11. A method according to Claim 1 , characterized in that said metal layer (140) is an anode layer.
12. A textile product having a fibrous structure (L) with photovoltaic property, characterized in that a photovoltaic coating (3) layer applied onto the fibrous structure (L) having undergone a twisting process (1 ) comprises at least one conductive layer (1 10), at least one continuous conductive layer (120), at least one photoactive heterojunction layer (130), at least one continuous conductive layer (120), and at least one metal layer (140).
13. A product according to Claim 12, characterized in that said fibrous structure (L) comprises a polymer-based material.
14. A product according to Claim 13, characterized in that said fibrous structure (L) comprises a polyamide surface or a polyester surface.
15. A product according to Claim 12, characterized in that said photovoltaic coating layer (3) has an organic structure.
16. A product according to Claim 12, characterized in that said photovoltaic coating (3) layer has a thickness of 1 -1000 nm.
17. A product according to Claim 12, characterized in that said conductive layer (1 10) is a cathode layer.
18. A product according to Claim 12, characterized in that said conductive layer (1 10) is an anode layer.
19. A product according to Claim 12, characterized in that said continuous conductive layer (120) is an electron transmission layer.
20. A product according to Claim 12, characterized in that said continuous conductive layer (120) is a positive charge layer.
21. A product according to Claim 12, characterized in that said metal layer (140) is a cathode layer.
22. A product according to Claim 12, characterized in that said metal layer (140) is an anode layer.
PCT/EP2013/073095 2012-11-08 2013-11-06 Production method for fibrous products having a photovoltaic structure WO2014072307A1 (en)

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