WO2009133163A2 - Modules photovoltaïques contenant des feuilles plastifiées ayant fonction de couche intermédiaire, à base d'acide silicique - Google Patents

Modules photovoltaïques contenant des feuilles plastifiées ayant fonction de couche intermédiaire, à base d'acide silicique Download PDF

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Publication number
WO2009133163A2
WO2009133163A2 PCT/EP2009/055243 EP2009055243W WO2009133163A2 WO 2009133163 A2 WO2009133163 A2 WO 2009133163A2 EP 2009055243 W EP2009055243 W EP 2009055243W WO 2009133163 A2 WO2009133163 A2 WO 2009133163A2
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WO
WIPO (PCT)
Prior art keywords
polyvinyl acetal
plasticizer
films
photovoltaic module
module according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2009/055243
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German (de)
English (en)
Other versions
WO2009133163A3 (fr
Inventor
Andreas Karpinski
Uwe Keller
Holger Stenzel
Martin Steuer
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Kuraray Europe GmbH
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Kuraray Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2009133163A2 publication Critical patent/WO2009133163A2/fr
Publication of WO2009133163A3 publication Critical patent/WO2009133163A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • 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

Definitions

  • the invention relates to the production of photovoltaic modules using plasticized films based on polyvinyl acetal containing SiO 2 , to prevent corrosion of the photosensitive semiconductor layers.
  • Photovoltaic modules consist of a photosensitive semiconductor layer, which is provided to protect against external influences with a transparent cover.
  • a photosensitive semiconductor layer monocrystalline solar cells or polycrystalline, thin semiconductor layers can be used on a support.
  • Thin-film solar modules consist of a photosensitive semiconductor layer deposited on a substrate such as a substrate. a transparent plate or a flexible carrier sheet e.g. by vapor deposition, vapor deposition, sputtering or wet deposition is applied.
  • Both systems are often placed between a sheet of glass and a rigid, rear cover plate, e.g. laminated from glass or plastics using a transparent adhesive.
  • the transparent adhesive must completely enclose the photosensitive semiconductor layer and its electrical connection lines, be UV-stable and insensitive to moisture and be completely bubble-free after the lamination process.
  • Curing resins or crosslinkable systems based on ethylene-vinyl acetate (EVA) are frequently used as transparent adhesives, as disclosed, for example, in DE 41 22 721 C1 or DE 41 28 766 A1. These adhesive systems can be set in the uncured state so low viscosity that they surround the solar cell units bubble-free. After adding a hardener or crosslinking agent, a mechanically resistant adhesive layer is obtained.
  • a disadvantage of these adhesive systems is that the hardening process often releases aggressive substances, such as acids, which release the Photosensitive semiconductor layers, in particular thin-film modules, can destroy.
  • some casting resins tend after some years to blistering or delamination by UV radiation.
  • thermosetting adhesive systems are the use of plasticized films based on polyvinyl acetals, such as polyvinyl butyral (PVB) known from the manufacture of laminated glass.
  • PVB polyvinyl butyral
  • Photovoltaic modules are subjected to a multitude of tests according to IEC 61215 (damp heat test, wet leakage current test) in order to reduce the leakage currents of the modules.
  • the electrical resistance of PVB films drops steeply with increasing moisture content, which strongly favors the occurrence of leakage currents in photovoltaic modules.
  • the films are open as encapsulating material to the environment and exposed to environmental conditions such as high ambient humidity.
  • the water content of the films in the edge region can increase sharply and assume values up to the equilibrium moisture content (about 3% by weight).
  • the raised Water content in the edge area of the film greatly reduces its electrical resistance in this area.
  • the photosensitive semiconductor layers can not be laid as far as the edge area of the film or module in order to avoid leakage currents. This reduces the area occupancy and thus the current efficiency of the module.
  • Solar cells in particular photosensitive semiconductor layers of thin-film solar modules, e.g. based on CIS (Copper / indium / (di) selenite) or
  • Copper / indium / gallium / sulphide / selenite (CIGS) or the thin conductive layers (TCO) are chemically susceptible to corrosion, so the encapsulant must be chemically inert and free from aggressive chemicals Additives such as crosslinkers, crosslinkers or primers, and the presence of water or traces of acid should be avoided.
  • the object of the present invention was therefore to provide plasticized films based on polyvinyl acetal with a low tendency to corrosion in relation to photosensitive semiconductor layers or the electrical conductors used.
  • films based on polyvinyl acetals containing SiO 2 have a reduced tendency to corrode the photosensitive semiconductor layers or the electrical conductors used.
  • the reduced tendency to corrosion may be due to the absorption of diffused moisture from the SiO 2 particles and not being available for cleavage of the residual acetate groups of the polyvinyl acetal into acetic acid and polyvinyl alcohol groups.
  • the present invention therefore photovoltaic modules, comprising a laminate of a) a transparent front cover b) one or more photosensitive semiconductor layers c) at least one plasticizer-containing polyvinyl acetal based film and d) a rear cover wherein the plasticizer-containing, based on polyvinyl acetal Film c) contains 0.01-5 wt.% SiO 2 (based on the film mixture).
  • the plasticizer-containing films based on polyvinyl acetal preferably contain 0.01 to 2.5% by weight, preferably 0.01 to 1% by weight, of SiO 2
  • Films according to the invention therefore have a light transmission TL (380-780 nm) according to EN 410 of more than 90%, preferably more than 95%.
  • the films used in the invention in a
  • Ambient humidity of 85% RH at 23 ° C a resistivity of at least 1 E + 11 ohm * cm, preferably at least 5E + 11 ohm * cm, preferably 1 E + 12 ohm * cm, preferably 5E + 12 ohm * cm, preferably 1 E + 13, preferably 5E + 13 ohm * cm, preferably 1E + 14 ohm * cm.
  • polyvinyl alcohol is dissolved in water and acetalized with an aldehyde such as butyraldehyde with the addition of an acid catalyst.
  • the precipitated polyvinyl acetal is separated, washed neutral, optionally suspended in an alkaline aqueous medium, then washed neutral again and dried.
  • the acid used for the acetalization must after the reaction be neutralized again. If an excess of base (eg NaOH, KOH or Mg (OH) 2 ) is used here, the alkalititer increases and all or part of the addition of the basic substance can be dispensed with.
  • base eg NaOH, KOH or Mg (OH) 2
  • the polyvinyl alcohol content of the polyvinyl acetal can be adjusted by the amount of aldehyde used in the acetalization.
  • Aldehydes having 2-10 carbon atoms e.g., valeraldehyde.
  • the films based on plasticized polyvinyl acetal preferably contain uncrosslinked polyvinyl butyral (PVB), which is obtained by acetalization of polyvinyl alcohol with butyraldehyde.
  • PVB polyvinyl butyral
  • crosslinked polyvinyl acetals in particular crosslinked polyvinyl butyral (PVB) is also possible.
  • Suitable crosslinked polyvinyl acetals are e.g. in EP 1527107 B1 and WO 2004/063231 A1 (thermal self-crosslinking of polyvinyl acetals containing carboxyl groups), EP 1606325 A1 (polyvinyl acetals crosslinked with polyaldehydes) and WO 03/020776 A1 (polyvinyl acetals crosslinked with glyoxylic acid).
  • EP 1527107 B1 and WO 2004/063231 A1 thermal self-crosslinking of polyvinyl acetals containing carboxyl groups
  • EP 1606325 A1 polyvinyl acetals crosslinked with polyaldehydes
  • WO 03/020776 A1 polyvinyl acetals crosslinked with glyoxylic acid
  • polyvinyl alcohol terpolymers of hydrolyzed vinyl acetate / ethylene copolymers can be used in the present invention. These compounds are typically hydrolyzed to greater than 98 mole percent and contain from 1 to 10 weight percent ethylene based units (e.g., "Exceval" type from Kuraray Europe GmbH).
  • hydrolyzed copolymers of vinyl acetate and at least one further ethylenically unsaturated monomer can also be used in the context of the present invention.
  • polyvinyl alcohols can be used in the context of the present invention, pure or as a mixture of polyvinyl alcohols with different degrees of polymerization or degree of hydrolysis.
  • Polyvinyl acetals still contain in addition to the acetal units
  • the polyvinyl acetals used according to the invention preferably have one Polyvinyl alcohol content of less than 22 wt.%, 20 wt.% Or 18 wt.%, Less than 16 wt.% Or 15 wt.% And in particular less than 14 wt.% To.
  • a polyvinyl alcohol content of 12% by weight should not be exceeded.
  • Polyvinyl acetal is preferably less than 3% by weight or less than 1% by weight, more preferably less than 0.75% by weight, very preferably less than 0.5% by weight and in particular less than 0.25% by weight.
  • the films have a plasticizer content of at most 40% by weight, 35% by weight, 32% by weight, 30% by weight, 28% by weight, 26% by weight, 24% by weight or 22% by weight. on, with a plasticizer content of 15 wt.% Should not be exceeded for reasons of processability of the film (each based on the total film formulation).
  • Inventive films or photovoltaic modules may contain one or more plasticizers.
  • Suitable plasticizers for the films used according to the invention are one or more compounds selected from the following groups:
  • Esters of polyhydric aliphatic or aromatic acids e.g. Dialkyladipates such as Dihexyladipat, Dioctyladipat, Hexylcyclohexyladipat, mixtures of heptyl and nonyl adipates, Diisononyladipat, heptylnonyl adipate and esters of adipic acid with cycloaliphatic or ether-containing ester alcohols, dialkyl sebacates such as dibutyl sebacate and esters of sebacic acid with cycloaliphatic or ether-containing ester alcohols, esters of phthalic acid such as butyl benzyl phthalate or bis-2-butoxyethyl phthalate
  • esters of di-, tri- or Tetraglykolen with linear or branched ali-phatic or cycloaliphatic Carboxylic acids may serve diethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylhexanoate), tri-ethylene glycol bis (2-ethylbu-ta-no-ate) .
  • Phosphates with aliphatic or aromatic ester alcohols e.g. Tris (2-ethylhexyl) phosphate (TOF), triethyl phosphate, diphenyl-2-ethylhexyl phosphate, and / or tricresyl phosphate
  • plasticizers for the films used according to the invention are one or more compounds selected from the following group: di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl adipate (DOA), dihexyl adipate (DHA), dibutyl sebacate (DBS), Triethylene glycol bis-n-heptanoate (3G7), tetraethylene glycol bis-n-heptanoate (4G7), triethylene glycol bis-2-ethylhexanoate (3GO or 3G8) tetraethylene glycol bis-n-2-ethylhexanoate (4GO or 4G8) Di-2-butoxy-ethyl adipate (DBEA), di-2-butoxyethoxyethyl adipate (DBEEA) di-2-butoxyethyl sebacate (DBES), di-2-ethylhexyl phthalate (DOP), di-isononyl phthalate
  • Plasticizers whose polarity expressed by the formula 100 ⁇ O / (C + H) is less than or equal to 9.4 are particularly suitable as plasticizers for the films used according to the invention, where O, C and H are the number of oxygen atoms. , Carbon and hydrogen atoms in each molecule.
  • the following table shows plasticizers which can be used according to the invention and their polarity values according to the formula 100 ⁇ O / (C + H).
  • the small amounts of Al 2 O 3 , TiO 2 , ZrO 2 and / or MgO in an amount of 0.1 to 20 wt.% contains.
  • the refractive index of the SiO 2 is approximated to that of the plasticized polyvinyl acetal. Materials of this kind are available from Evonik Degussa GmbH.
  • a further possibility for reducing the tendency of the films used according to the invention to resist photosensitive semiconductor layers is the avoidance of traces of acid.
  • a further possibility for reducing the tendency of the films used according to the invention to resist photosensitive semiconductor layers is the avoidance of acid traces in the production of the material.
  • Films of this type are generally prepared by extrusion at elevated temperatures, whereby a thermal decomposition of the polymeric material or the plasticizer may occur. Furthermore, by diffused water cleavage of the residual acetate groups of the polyvinyl alcohol occur, whereby acetic acid is released. In both cases, acid traces that can attack the photosensitive semiconductor layers result.
  • the films used according to the invention therefore preferably have a certain basicity, expressed as alkali titers, which should be above 5 or 10, preferably above 15 and in particular above 20, 30 or 40. A maximum alkali titre of 100 should not be exceeded.
  • the alkali titer is, as described below, by back titration the film is determined and can be adjusted by adding basic substances, such as metal salts of organic carboxylic acids having 1 to 15 carbon atoms, in particular alkali metal or alkaline earth metal salts such as magnesium or potassium acetate.
  • the basic compound is usually used in a concentration of 0.005 to 2% by weight, in particular 0.05 to 1% by weight, based on the total mixture.
  • the films of the invention may additionally contain conventional additives, such as oxidation stabilizers, UV stabilizers, dyes, pigments and anti-adhesive.
  • the lamination of the photovoltaic modules is carried out under fusion of the films, so that a bubble and schlierenoker inclusion of the photosensitive semiconductor layer is obtained with the films.
  • the photosensitive semiconductor layers are applied to the cover d) (for example by vapor deposition, vapor deposition, sputtering or wet deposition) and bonded by a film c) to the transparent front cover a).
  • the photosensitive semiconductor layers are applied to the transparent front cover a) and glued by the film c) with the rear cover d).
  • the photosensitive semiconductor layers between two films c) embedded and so with the covers a) and d) are glued.
  • Foils are usually 0.38, 0.51, 0.76, 1.14, 1.52 or 2.28 mm.
  • the transparent front cover a) is usually made of glass or PMMA.
  • the back cover d) (so-called backsheet) of the photovoltaic module according to the invention may consist of glass, plastic or metal or their composites, wherein one of the carriers may be transparent. It is also possible to use one or both covers as composite glazing (ie as a laminate of at least two glass panes and at least one PVB foil) or as insulating glazing with a gas gap. Of course, the combination of these measures is possible.
  • the photosensitive semiconductor layers used in the modules need not have any special properties. Mono-, polycrystalline or amorphous systems can be used.
  • the photosensitive semiconductor layer is applied directly to a support.
  • An encapsulation is not possible here. Therefore, the laminated body of a support (e.g., the back cover) having the photosensitive semiconductor layer and the transparent front cover is collapsed by at least one interposed plasticized polyvinyl acetal based film of the present invention and adhered thereto at an elevated temperature.
  • the photosensitive semiconductor layer may be applied to the transparent front cover as a carrier and bonded to the back cover by at least one interposed plasticized polyvinyl acetal based film of the present invention.
  • Photovoltaic modules used vacuum laminators. These consist of a heatable and evacuable chamber in which Laminated glazing can be laminated within 30 - 60 minutes. Reduced pressures of 0.01 to 300 mbar and temperatures of 100 to 200 0 C, in particular 130 - 160 0 C have proven in practice.
  • a laminated as described above laminated body between at least one pair of rollers at a temperature of 60 to 150 ° C are pressed into a module according to the invention.
  • Systems of this type are known for the production of laminated glazing and usually have at least one heating tunnel before or after the first press shop in systems with two pressing plants.
  • the invention further provides for the use of plasticized polyvinyl acetal-based films c) which contain 0.01 to 5% by weight SiO 2 , or with the cited preferred embodiments for the production of photovoltaic modules.
  • Photovoltaic modules according to the invention can be used as a facade component
  • the measurement of the volume resistivity of the film is carried out according to DIN IEC 60093 at a defined temperature and ambient humidity (23 ° C and 85% rl_F) after the film has been conditioned for at least 24 hours under these conditions.
  • a plate electrode type 302 132 from Fetronic GmbH and an ohmmeter ISO-Digi 5 kV from Amprobe were used.
  • the test voltage was 2.5kV, the waiting time after application of the test voltage up to the data acquisition 60 sec.
  • Polyvinyl acetals were determined according to ASTM D 1396-92. The analysis of the metal ion content was carried out by atomic absorption spectroscopy (AAS).
  • the water or moisture content of the films is with the
  • Karl Fischer method determined This method can be carried out both on the unlaminated film and on a laminated photovoltaic module as a function of the distance to the edge of the film.
  • the steam-heat test is carried out in accordance with IEC 61646.
  • Substrate glasses of dimension 30 ⁇ 30 cm with deposited, functionally contacted thin-layer cells (CIS) were glued in the laminator process with a cover slip through PVB films. After a first light-soak treatment (equilibration), the output power (photocurrent yield) of the test modules was determined. After 1000h steam-heat exposure (85% RH, 85 ° C) was re-equilibrated and the photocurrent yield determined.
  • Photovoltaic modules can by Randeinflalle, such as
  • modules can lose some of their power. This relates to the modules according to the invention and the comparison modules to the same extent.

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  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de feuilles à base de polyvinylacétale, contenant des plastifiants, qui contiennent du SiO2, pour produire des modules photovoltaïques.
PCT/EP2009/055243 2008-04-30 2009-04-30 Modules photovoltaïques contenant des feuilles plastifiées ayant fonction de couche intermédiaire, à base d'acide silicique Ceased WO2009133163A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008001502A DE102008001502A1 (de) 2008-04-30 2008-04-30 Photovoltaikmodule mit Kieselsäure-haltigen plastifizierten Zwischenschicht-Folien
DE102008001502.4 2008-04-30

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Publication Number Publication Date
WO2009133163A2 true WO2009133163A2 (fr) 2009-11-05
WO2009133163A3 WO2009133163A3 (fr) 2010-08-19

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DE (1) DE102008001502A1 (fr)
TW (1) TW201009005A (fr)
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WO2011058026A1 (fr) * 2009-11-11 2011-05-19 Kuraray Europe Gmbh Vitrages composites avec des feuilles contenant un plastifiant à faible tendance au fluage
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WO2011058026A1 (fr) * 2009-11-11 2011-05-19 Kuraray Europe Gmbh Vitrages composites avec des feuilles contenant un plastifiant à faible tendance au fluage
EP2325001A1 (fr) * 2009-11-11 2011-05-25 Kuraray Europe GmbH Vitrifications composites dotées de feuilles contenant du plastifiant et ayant un faible fluage
WO2013000894A3 (fr) * 2011-06-28 2013-03-21 Saint-Gobain Glass France Procédé de stabilisation rapide du rendement nominal d'un module solaire à couche mince
US9024175B2 (en) 2011-06-28 2015-05-05 Saint-Gobain Glass France Method for quickly stabilizing the nominal output of a thin-film solar module
WO2018055107A1 (fr) * 2016-09-26 2018-03-29 Henkel Ag & Co. Kgaa Composition dispersible fusible ayant une viscosité indépendante de la température

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