MX2012010354A - Photovoltaic module with stabilized polymer. - Google Patents

Photovoltaic module with stabilized polymer.

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Publication number
MX2012010354A
MX2012010354A MX2012010354A MX2012010354A MX2012010354A MX 2012010354 A MX2012010354 A MX 2012010354A MX 2012010354 A MX2012010354 A MX 2012010354A MX 2012010354 A MX2012010354 A MX 2012010354A MX 2012010354 A MX2012010354 A MX 2012010354A
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MX
Mexico
Prior art keywords
poly
vinyl butyral
layer
benzotriazole
photovoltaic device
Prior art date
Application number
MX2012010354A
Other languages
Spanish (es)
Inventor
Weihong Cui
Original Assignee
Solutia Inc
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Filing date
Publication date
Application filed by Solutia Inc filed Critical Solutia Inc
Publication of MX2012010354A publication Critical patent/MX2012010354A/en

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    • 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
    • B32B17/10678—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 comprising UV absorbers or stabilizers, e.g. antioxidants
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0376—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
    • H01L31/03762—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors including only elements of Group IV of the Periodic System
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV 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

Abstract

The present invention provides a photovoltaic device comprising metal and a poly(vinyl butyral) layer that incorporates a suitable amount of lH-benzotriazole. When electrical bias is applied to the photovoltaic device, lH-benzotriazole forms a barrier layer at the metal/poly(vinyl butyral) interface, which, for example, unexpectedly virtually eliminated the yellowing of poly(vinyl butyral) in photovoltaic devices comprising silver components.

Description

PHOTOVOLTAIC MODULE WITH STABILIZED POLYMER FIELD OF THE INVENTION The present invention belongs to the field of photovoltaic modules and, specifically, the present invention pertains to the field of thin film photovoltaic modules that incorporate a polymeric layer and a photovoltaic device on a suitable thin film photovoltaic substrate.
BACKGROUND OF THE INVENTION Currently there are two common types of photovoltaic (solar) modules in use. The first type of photovoltaic module uses a semiconductor wafer as a substrate and the second type of photovoltaic module uses a thin semiconductor film which is deposited on a suitable substrate.
The semiconductor wafer type photovoltaic modules typically comprise the crystalline silicon wafers which are commonly used in various solid state electronic devices, such as computer memory chips and computer processors.
Thin-film photovoltaic modules can incorporate one or more conventional semiconductors, such as amorphous silicon, onto a suitable substrate. Unlike chip applications, in which a chip is cut from an ingot, thin film photovoltaic modules are formed using comparatively simple deposition techniques such as spray coating, physical vapor deposition (PVD), by their acronyms in English) or chemical vapor deposition (CVD, for its acronym in English).
Thin film photovoltaic modules typically incorporate a layer of ethylene-vinyl acetate copolymer (EVA) or a layer of poly (vinyl butyral) (PVB) to seal and protect the underlying photovoltaic device. The reliable long-term operation of the photovoltaic module is, of course, extremely important and, therefore, the stability of the polymer layer is a fundamental factor for any specific photovoltaic device.
Although EVA has been used extensively in photovoltaic modules, the use of poly (vinyl butyral) is very desirable because it does not present the same disadvantages as EVA, such as degradation by acetic acid, as detailed in the United States Patent Publication. 2007/0259998.
Although it is often preferable to employ poly (vinyl butyral), it has been found that the poly (vinyl butyral) turns yellow when in contact with silver-containing elements.
Accordingly, poly (vinyl butyral) compositions that are suitable for long-term stable use in photovoltaic modules containing metallic elements are needed in the art.
SUMMARY OF THE INVENTION The present invention provides a photovoltaic device comprising metal and a layer of poly (vinyl butyral) which incorporates a suitable amount of 1H benzotriazole. When electric polarization is applied to the photovoltaic device, the 1H benzotriazole forms a barrier layer at the metal / poly (vinyl butyral) interface, which, for example, unexpectedly virtually eliminates the yellowing of poly (vinyl butyral) in photovoltaic devices that They comprise silver components.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 represents a schematic cross-sectional view of a thin film photovoltaic device of the present invention.
DETAILED DESCRIPTION The thin film photovoltaic devices of the present invention include a layer of poly (vinyl butyral) formulated according to the description herein, which provides excellent adhesion, strength, sealing, processability and durability to the photovoltaic device and comprising 1H benzotriazole.
One embodiment of a thin film photovoltaic module of the present invention is shown in Figure 1 generally as 10. As shown in the Figure, a photovoltaic device 14 is formed on a base substrate 12, which may be, for example, glass or plastic. A protective substrate 18 is attached to the photovoltaic device 14 with a layer of poly (vinyl butyral) 16.
As used herein, "1H benzotriazole" refers to the compound shown in the following formula: 1 H benzotriazole may be included in the poly (vinyl butyral) layer in any suitable amount and, in various embodiments, 1 H benzotriazole is included, as a percentage by weight, of 0.001 to 5%, 0.01 to 5%, 0, 1 to 5%, 1 to 5%, 2 to 5% or 0.1 to 0.4%.
The 1H benzotriazole is preferably included in the poly (vinyl butyral) at the time of formation of a polymeric layer through the melting composition of the 1H benzotriazole with the poly (vinyl butyral) resin and any other additive. The 1H benzotriazole may also be provided in the form of a salt, for example, sodium, potassium and ammonium. 1H benzotriazole is a known corrosion inhibitor for copper, silver, cobalt, aluminum and zinc. It is marketed by PMC Specialties Group and sold under the trademark Cobratec 99. Other corrosion inhibitors that are useful for photovoltaic devices of the present invention include: 1H-benzotriazole derivatives such as 5-methyl-1H-benzotriazole, 5-carboxybenzotriazole and other alkyl derivative of 1H benzotriazole; imidazole and imidazole derivatives such as benzimidizole, 5,6-dimethylbenzimdiazole, 2-mercaptobenzoimidazole and fatty acid derivatives of 4,5-dihydro-? imidazole; thiadiazole and thiadiazole alkyl derivatives such as 2-mercaptobenzothiazole, 1,2-bis (phenylthio) ethane, 2,5-bis (n-octyldithio) -1,4,4-thiadiazole, 2-amino, 5-mercapto, 1,3,4-thiadizole, 2 mercaptopyrimidine, 2-mercaptobenzoxazole; histamine; histidine; and 2 aminopyrimidine.
Additional additives Additional additives that may be included in polymer layers of the present invention to improve stability and performance include metal passivators such as Irganox MD 1024® (CAS 32687 78 8) and Naugard XL 1® (CAS 70331 94 1), light stabilizers blocked amine such as Tinuvin 123® (CAS129757 67 1) and phenolic antioxidants such as Anox 70® (2,2'-thiodiethylene bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] CAS 41484 35 9).
It is expected that the combination of any of the above polymeric stabilizers with benzotriazole will achieve additional stability of poly (vinyl butyral) at the poly (vinyl butyral) -metal interface and within the polymer. Experimental data have suggested that the addition of benzotriazole and Anox 70® in a poly (vinyl butyral) formulation in fact further reduces polymeric discoloration and protects the structure of thin-film solar panels. In various embodiments of the present invention, 1 H benzotriazole and a phenolic antioxidant are incorporated into a layer of poly (vinyl butyral) and, in some embodiments, 1 H benzotriazole and 2,2'-tiodiethylene bis [3- (3, 5 -di-t-butyl-4-hydroxyphenyl) propionate to a layer of poly (vinyl butyral).
Poly (vinyl butyral) layer The thin film photovoltaic modules of the present invention utilize a layer of poly (vinyl butyral) as the lamination adhesive that is used to seal the photovoltaic device to a protective substrate, thereby forming the photovoltaic module of the present invention.
The poly (vinyl butyral) of the present invention can be produced by acetalization processes, such as are known in the art (see, for example, U.S. Patent Nos. 2,282,057 and 2,282,026). In one embodiment, the solvent method described in Vinyl Acetal Polymers, in the Encyclopedia of Polymer Science & Technology, 3rd edition, Volume 8, pages 381-399, by B.E. Wade (2003). In another embodiment, the aqueous method described therein can be used. Poly (vinyl butyral) is commercially available in various forms, for example, from Solutia Inc., St. Louis, Mo., as Butvar ™ resin.
In various embodiments, the poly (vinyl butyral) comprises 10 to 35 weight percent (% p.) Of hydroxyl groups calculated as poly (vinyl alcohol), 13 to 30% p. of hydroxyl groups calculated as poly (vinyl alcohol) or 15 to 22% p. of hydroxyl groups calculated as poly (vinyl alcohol). The polymeric layer resin may also comprise less than 15% p. of residual ester groups, 13% p.; ll% p., 9% p., 7% p., 5% p. or less than 3% p. of residual ester groups calculated as polyvinyl acetate, the remainder being an acetal, preferably butyraldehyde acetal, but optionally including other acetal groups in lesser amount, for example, a 2-ethyl hexanal group (see, for example, U.S. Pat. No. 5,137,954).
In various embodiments, the poly (vinyl butyral) has a molecular weight of at least 30,000, 40,000, 50,000, 55,000, 60,000, 65,000, 70,000, 120,000, 250,000 or at least 350,000 grams per mole (g / mol or Daltons). Small amounts of a dialdehyde or trialdehyde may also be added during the acetalization step to increase the molecular weight to at least 350,000 g / mol (see, for example, U.S. Patent Nos. 4,902,464; 4,874,814; 4,814,529; and 4,654,179). As used herein, the term "molecular weight" means the weight average molecular weight.
Various adhesion control agents can be used in the polymeric layers of the present invention, including sodium acetate, potassium acetate and magnesium salts. Magnesium salts that can be used with these embodiments of the present invention include, but are not limited to, those disclosed in U.S. Patent No. 5,728,472, such as magnesium salicylate, magnesium nicotinate, di- (2 magnesium di- (3-hydroxy-2-naptoate) and magnesium bis (2-ethyl butyrate) (chemical abstract number 79992-76-0). In various embodiments of the present invention the magnesium salt is magnesium bis (2-ethyl butyrate).
In various polymeric layer embodiments of the present invention, the polymeric layers may comprise 20 to 60, 25 to 60, 20 to 80, 10 to 70 or 10 to 100 parts of phr plasticizer. Obviously, other quantities may be used, as appropriate for the specific application. In some embodiments, the plasticizer has a hydrocarbon segment of less than 20, less than 15, less than 12, or less than 10 carbon atoms. The amount of plasticizer can be adjusted to affect the vitreous transition temperature (Tg) of the poly (vinyl butyral) layer. In general, larger amounts of plasticizer are added to lower the Tg.
Any suitable plasticizer can be added to the polymer resins of the present invention to form the polymer layers. The plasticizers used in the polymeric layers of the present invention can include esters of a polybasic acid or a polyhydric alcohol, among others. Suitable plasticizers include, for example, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexanoate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyldipate, mixtures of heptyl and nonyl adipates, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate, polymeric plasticizers such as oil-modified sebacic alkyds, phosphate and adipate mixtures such as those disclosed in U.S. Patent No. 3,841,890 , adipates such as those disclosed in U.S. Patent No. 4,144,217 and mixtures and combinations of the foregoing. Other plasticizers that can. used are mixed adipates made from C4 to C9 alkyl alcohols and C4 to CIO cycloalcohols, such as disclosed in U.S. Patent No. 5,013,779 and C6 to C8 adipate esters, such as hexyl adipate. In various embodiments, the plasticizer used is dihexyl adipate and / or triethylene glycol di-2-ethylhexanoate.
The poly (vinyl butyral) polymer, the plasticizer and any additive can be thermally processed and shaped into a sheet according to methods known to those skilled in the art. An exemplary method for forming a poly (vinyl butyral) sheet comprises extruding molten poly (vinyl butyral) comprising resin, plasticizer and additives, by passing the molten material through a matrix (e.g., a matrix having an aperture that is substantially greater in one dimension than in a perpendicular dimension).
Another exemplary method for forming a poly (vinyl butyral) sheet comprises casting the molten material of a matrix on a roll, solidifying the resin and subsequently removing the solidified resin as a sheet. In various embodiments, the polymer layers may have a thickness of, for example, 0.1 to 2.5 millimeters, 0.2 to 2.0 millimeters, 0.25 to 1.75 millimeters, and 0.3 to 1.5 millimeters. millimeters The poly (vinyl butyral) layers of the present invention may include low molecular weight epoxy additives. Any suitable epoxy agents can be used in the present invention, such as are known in the art (see, for example, U.S. Patent Nos. 5,529,848 and 5,529,849).
Other additives may be incorporated into the polymeric sheet to improve its performance in a final product. Such additives include, but are not limited to, dyes, pigments, stabilizers (eg, ultraviolet stabilizers), antioxidants, anti-blocking agents, additional IR absorbers, flame retardant, combinations of the foregoing additives and the like, as are known in the art. .
Typical ultraviolet stabilizers include substituted 2H-benzotriazoles, such as those marketed by Ciba Specialty Company under the trademark Tinuvin®, for example, Tinuvin 328®, as shown in Formula II: Formula i) Substrate base The base substrates of the present invention, which are shown as element 12 in Figure 1, can be any suitable substrate on which the photovoltaic devices of the present invention can be formed. Examples include, but are not limited to, glass and rigid plastic glazing materials that provide "rigid" thin film modules and thin plastic films such as poly (ethylene terephthalate), polyimides, fluoropolymers, and the like, which provide thin film modules " flexible " It is generally preferred that the base substrate allows the transmission of most of the incident radiation in the range of 350 to 1200 nanometers, but those skilled in the art will recognize that there are possible variations, including variations in which light enters the photovoltaic device through the protective substrate.
Thin film photovoltaic device The thin film photovoltaic devices of the present invention, which are shown as the element 14 in Figure 1, are formed directly on the base substrate. Typical fabrication of the device involves the deposition of a first conductive layer, etching of the first conductive layer, deposition and etching of semiconductor layers, deposition of a second conductive layer, etching of the second conductive layer and application of conductors for bars and protective layers , depending on the application. Optionally, an electrically insulating layer can be formed on the base substrate between the first conductive layer and the base substrate. This optional layer can be, for example, a layer of silicon.
Although the 1H benzotriazole agent of the present invention can be added to polymeric layers for use in silver-free photovoltaic devices, in preferred embodiments, the 1H benzotriazole is used in a layer of poly (vinyl butyral) which is used in a photovoltaic module which it has a photovoltaic device comprising silver. Examples of silver components include, but are not limited to, layers or conductive elements (such as wire grid) or reflective layers (see, for example, US2006 / 0213548).
In other embodiments, the 1H benzotriazole agent of the present invention may be added to the polymeric layers for use in photovoltaic devices comprising other metals that are subject to degradation, including, for example, bismuth, copper, cadmium, lead, tin, zinc , gold, indium, palladium, platinum, aluminum, antimony, chromium, iron, nickel, rhodium, tantalum, titanium or vanadium.
Those skilled in the art will recognize that the foregoing description of the manufacture of the device is only one known method and is only one embodiment of the present invention. Many different types of thin film photovoltaic devices are within the scope of the present invention. Examples of training methods and devices include those described in U.S. Patent Documents 2003/0180983, 7,074,641, 6,455,347, 6,500,690, 2006/0005874, 2007/0235073, 7,271,333 and 2002/0034645.
The various components of the thin film photovoltaic device can be formed by any suitable method. In various embodiments, chemical vapor deposition (CVD), physical vapor deposition (PVD), and / or spraying can be used.
The two conductive layers described above serve as electrodes for carrying the current generated by the interleaved semiconductor material. One of the electrodes is typically transparent to allow solar radiation to reach the semiconductor material. Obviously, both conductors can be transparent or one of the conductors can be reflective, resulting in reflection of the light that has passed through the semiconductor material back into the semiconductor material. The conductive layers can comprise any suitable conductive oxide material, such as tin oxide or zinc oxide or if the transparency is not fundamental, such as for "background" electrodes, metal or metal alloy layers, such as the metal layers, can be used. which comprise aluminum or silver. In other embodiments, the metal oxide layer can be combined with the metal layer to form an electrode, and the metal oxide layer can be doped with boron or aluminum and deposited using chemical vapor deposition at low pressure. The conductive layers may have, for example, 0.1 to 10 micrometers in thickness.
The photovoltaic region of the thin film photovoltaic device may comprise, for example, hydrogenated amorphous silicon in a conventional PI or PN structure. The silicon typically can be up to about 500 nanometers thick, typically comprising a layer p having a thickness of 3 to 25 nanometers (a layer i of 20 to 450 nanometers and a layer n of 20 to 40 nanometers). luminescent discharge in silane or a mixture of silane and hydrogen, as described, for example, in U.S. Patent No. 4,064,521.
Alternatively, the semiconductor material can be micromorph silicon, cadmium telluride (CdTe or CdS / CdTe), indium copper diselenide, (CuInSe2 or "CIS" or CdS / CuInSe2), copper, indium and gallium selenide (CuInGaSe2 or "CIGS"). ") or other photovoltaically active materials. The photovoltaic devices of this invention may have additional semiconductor layers or combinations of the preceding semiconductor types and may have a serial, triple junction or heterounion structure.
The engraving of the layers to form the individual components of the device can be carried out using any conventional semiconductor manufacturing technique, including, but not limited to, screen printing with resistant stencils, etching with positive or negative photoresists, mechanical plotting, tracing by unloading electrical, chemical engraving or laser engraving. The etching of the various layers will typically result in the formation of individual photocells within the device. Said devices can be electrically connected to other devices using busbars that are inserted or formed at any suitable stage of the manufacturing process.
Optionally, a protective layer can be formed on the photocells before assembly with the poly (vinyl butyral) layer and the protective substrate. The protective layer can be, for example, powdered aluminum.
The electrically interconnected photocells formed from the optional insulating layer, the conductive layers, the semiconductor layers and the optional protective layer form the photovoltaic device of the present invention.
Protective substrate The protective substrates of the present invention, which are shown as the element 18 in Figure 1, can be any suitable substrate that can be used to bind to the polymeric layer and sufficiently protect the underlying device. The examples include, not limited to, glass, rigid plastic and thin plastic films such as poly (ethylene terephthalate), polyimides, fluoropolymers and the like. In general, it is preferred that the protective substrate allow the transmission of most of the incident radiation in the range of 350 to 1200 nanometers, but those skilled in the art will recognize that there are possible variations, including variations in which light enters the photovoltaic device through the base substrate. In these embodiments, it is not necessary that the protective substrate be transparent or for the most part not and can be, for example, a reflective film that prevents light from leaving the photovoltaic module through the protective substrate.
Ensamblaj e The final assembly of the thin film photovoltaic modules of the present invention involves arranging a layer of poly (vinyl butyral) in contact with a thin film photovoltaic device, with bus bars, if applicable, that has been formed on a base substrate, arranging a protective substrate in contact with the poly (vinyl butyral) layer and laminating the assembly to form the module.
Although the main body of this application has been described with the preferred embodiment exemplified, the present invention includes within its scope all photovoltaic devices comprising a silver and poly (vinyl butyral) component, including standard photovoltaic devices (without thin film). ), as well as other multilayer laminated materials comprising a polyvinyl butyral sheet in contact with a degradable metal component (e.g., solar glass and mirrors), which are known in the art.
The present invention includes poly (vinyl butyral) sheets having any of the components described herein and incorporating 1 H benzotriazole and, optionally, any additional additives as described herein.
The present invention includes a method for manufacturing a photovoltaic module, comprising the steps of providing a base substrate, forming a photovoltaic device of the present invention thereon and laminating the photovoltaic device with a protective substrate using a layer of poly (vinyl butyral) ) of the present invention.
The present invention includes photovoltaic modules comprising polymeric layers of the present invention.
EXAMPLES Example 1 Using a small extruder on a laboratory scale, 750 grams of poly (vinyl butyral) resin with a vinyl alcohol content of about 18.7% and a vinyl acetate residue of 0.5-4% p with 285 were mixed. grams of di- (2 ethylhexanoate) of triethylene glycol as a plasticizer, 2.63 grams of the Tinuvin 328® UV absorber, 0.19 grams of magnesium (2-ethylbutyrate) as an adhesion control salt and various additives as shown in Table 1 and extruded in sheets 0.76 millimeters thick.
The sheets were used to laminate a thin-film solar cell (15x15 centimeters). The laminates were exposed to 85 ° C with 85% relative humidity at 1000 volts of polarization for 1000 hours. The yellowness indexes of the laminated materials after the exposure of 1000 hours were measured. The yellowness index typical of laminate materials before exposure of approximately 12 (between 11 and 13).
Example 2 Sheets (1.14 mm thick) were prepared in the following manner in a pilot-scale extruder: for every 100 grams of poly (vinyl butyral) resin, se. they added 38 grams of di- (2-ethylhexanoate) of triethylene glycol as a plasticizer, 0.35 grams of Tinuvin 328®, 0.025 grams of magnesium (2-ethylbutyrate) and various additives as shown in Table 2. Glass was used coated with silver and other layers to prepare the laminated materials of poly (vinyl butyral). The size of the coated glass is 7x9 centimeters. The laminated materials were tested for 670 hours at 85 ° C, with 85% relative humidity (RH) and 1,000 volts of electric polarization.
Table 1 Table 2 Example 3 The concentration of silver in Control No. 2 and Sample 4 of Example 1 was determined after exposure for 1000 hours. The samples were delaminated. The plasticizer was removed from the layers by wetting and stirring in a mixture of 75:25 hexane / ethyl acetate. The recovered poly (vinyl butyral) resin retained the color and was then dissolved in acid and analyzed for silver content using a Perkin Elmer Optima 3300 DV instrument. A standard sheet of poly (vinyl butyral) was also analyzed to determine the silver content.
Table 3 The "yellowness index" was measured on intact glass laminate material. The sample was measured by hemispherical reflectance with the specular component excluded according to the sample method of ASTM E 1331 and where the clear surface of the glass is oriented towards the light source. Using the reflectance values throughout the visible spectrum, the value of the yellowness index was calculated using column "C, 1931" of "Coefficients of the Equations for Yello ness Index" presented in table 1 of the method ASTM E 313"Standard Test Method for Yellowness Index of Plastics ".
The evaluation under polarization is achieved by first forming the following construct: electrode / glass layer / photovoltaic film / electrode / poly (vinyl butyral) / glass layer. A voltage of 1,000 direct current is then applied, resulting in a current of approximately 0.1 milliamperes.
As shown in the examples, the addition of Tinuvin 328®, a substituted 2H-benzotriazole derivative shown in Formula II, does not prevent yellowing, highlighting the resounding success of 1H benzotriazole.
By virtue of the present invention, it is now possible to provide thin film photovoltaic modules which have excellent stability of poly (vinyl butyral) and resistance to yellowing when used with photovoltaic devices containing silver.
Although the invention has been described with reference to the exemplary embodiments, those skilled in the art will understand that various changes may be made and the equivalents may be replaced by elements thereof without departing from the scope of the invention. Additionally, many modifications can be made to adapt a specific situation or material to the teachings of the invention without departing from the essential scope thereof. Accordingly, it is intended that the invention not be limited to the specific embodiments disclosed as the best form contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Furthermore, it will be understood that any ranges, values or features provided for a single component of the present invention can be used interchangeably with any ranges, values or features provided for any of the other components of the invention, when compatible, to form a modality that has defined values for each of the components, such as are provided throughout the present. For example, thin film modules can comprise combinations of poly (vinyl butyral) and photovoltaic elements to form many permutations that are within the scope of the present invention, but which would be extremely cumbersome to list.
Any reference numbers of Figures provided within the summary or any claims are for illustrative purposes only and are not to be construed as limiting the claimed invention to any specific embodiment in any figure.
The figures are not drawn to scale unless otherwise indicated.
Each reference, including newspaper articles, patents, applications and books, mentioned herein are incorporated by reference herein in their entirety.

Claims (19)

1. A photovoltaic module comprising: a base substrate; a photovoltaic device arranged in contact with the base substrate, wherein the photovoltaic device comprises a metal component; a layer of poly (vinyl butyral) disposed in contact with the photovoltaic device, wherein the layer of poly (vinyl butyral) comprises IH benzotriazole or salt of IH benzotriazole; and a protective substrate disposed in contact with the poly (vinyl butyral) layer.
2. The module according to claim 1, characterized in that the photovoltaic device is a thin film photovoltaic device.
3. The module according to claim 2, characterized in that the poly (vinyl butyral) layer comprises 0.001 to 5 weight percent of IH benzotriazole.
4. The module according to claim 2, characterized in that the layer of poly (vinyl butyral) comprises 0.1 to 0.4 weight percent of IH benzotriazole.
5. The module according to claim 2, characterized in that the poly (vinyl butyral) layer comprises 1 to 5 weight percent of IH benzotriazole.
6. The module according to claim 2, characterized in that the poly (vinyl butyral) layer further comprises a phenolic antioxidant.
7. The module according to claim 2, characterized in that the metal is bismuth, copper, cadmium, lead, tin, zinc, silver, gold, indium, palladium, platinum, aluminum, antimony, chromium, iron, nickel, rhodium, tantalum, titanium or vanadium.
8. The module according to claim 2, characterized in that the metal is silver.
9. The module according to claim 2, characterized in that the metallic component is used as the conductive layer.
10. A polymeric interlayer layer comprising a poly (vinyl butyral) sheet comprising 0.001 to 5 weight percent of 1H benzotriazole.
11. The interleaved layer according to claim 10, characterized in that the poly (vinyl butyral) sheet comprises 0.1 to 0.4 weight percent of 1H benzotriazole.
12. The interleaved layer according to claim 10, characterized in that the poly (vinyl butyral) sheet comprises 1 to 5 weight percent of 1H benzotriazole.
13. The interleaved layer according to claim 10, characterized in that the poly (vinyl butyral) sheet further comprises a phenolic antioxidant.
14. A multilayer laminate material comprising a first substrate; a metal component disposed in contact with the first substrate; a layer of poly (vinyl butyral) disposed in contact with the metal component, wherein the layer of poly (vinyl butyral) comprises 1 H benzotriazole or 1 H benzotriazole salt; and a second substrate disposed in contact with the poly (vinyl butyral) layer.
15. The multilayer laminate material according to claim 14, characterized in that the poly (vinyl butyral) sheet comprises 0.1 to 0.4 weight percent of 1H benzotriazole.
16. The multilayer laminate material according to claim 14, characterized in that the poly (vinyl butyral) sheet comprises 1 to 5 weight percent of 1H benzotriazole.
17. The multilayer laminate material according to claim 14, characterized in that the poly (vinyl butyral) sheet comprises 0.001 to 5 weight percent of 1H benzotriazole.
18. The multilayer laminate material according to claim 14, characterized in that the poly (vinyl butyral) sheet further comprises a phenolic antioxidant.
19. A method for manufacturing a photovoltaic module, comprising: providing a base substrate; forming a photovoltaic device on the base substrate, wherein the photovoltaic device comprises a metal component; arranging a layer of poly (vinyl butyral) in contact with the photovoltaic device, wherein the layer of poly (vinyl butyral) comprises 1 H benzotriazole or 1 H benzotriazole salt; arranging a protective substrate in contact with the poly (vinyl butyral) layer; and laminating the base substrate, the photovoltaic device, the poly (vinyl butyral) layer and the protective substrate to form the module.
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