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WO2013107818A1 - Ethylene-(meth)acrylic-acid-copolymers for solar cell laminates - Google Patents

Ethylene-(meth)acrylic-acid-copolymers for solar cell laminates Download PDF

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Publication number
WO2013107818A1
WO2013107818A1 PCT/EP2013/050843 EP2013050843W WO2013107818A1 WO 2013107818 A1 WO2013107818 A1 WO 2013107818A1 EP 2013050843 W EP2013050843 W EP 2013050843W WO 2013107818 A1 WO2013107818 A1 WO 2013107818A1
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WIPO (PCT)
Prior art keywords
polymer
solar cell
copolymer
din
ethylene
Prior art date
Application number
PCT/EP2013/050843
Other languages
French (fr)
Inventor
Szilard Csihony
Ivette Garcia Castro
Sven Fleischmann
Bernd DÜTTRA
Original Assignee
Basf Se
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Publication date
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Publication of WO2013107818A1 publication Critical patent/WO2013107818A1/en

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Classifications

    • 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
    • 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
    • B32B17/10009—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 number, the constitution or treatment of glass sheets
    • B32B17/10018—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 number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B17/10743—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 acrylate (co)polymers or salts thereof
    • 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
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10871—Making laminated safety glass or glazing; Apparatus therefor by pressing in combination with particular heat treatment
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • 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

Definitions

  • the invention relates to solar cell modules, laminates composed of solar cell elements encapsulated within a polymer composition of a copolymer of ethylene and an ethyl- enically unsaturated carboxylic acid, compositions which comprise semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements; and a copolymer of ethylene and an ethylenically unsaturated carboxylic acid, a process for the preparation of electric energy generating laminates, and the use of an uncross- linked polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid for encapsulating semi-conductors.
  • modules comprising electronic devices, such as solar cells, also known as photo-voltaic cells, liquid crystal panels, electro-luminescent devices and plasma display units.
  • modules often comprise an electronic device in combination with one or more substrates, e.g. glass cover sheets, often positioned between two substrates in which one or both of the substrates comprise glass, metal, plastic, rubber or another material.
  • the polymers are typically used as encapsulants or sealants for the module or, depen- ding on the design of the module, as a skin layer component of the module, e.g. a back-skin in a solar cell module.
  • Typical polymers include silicone resins, epoxy resins, polyvinyl butyral resins, cellulose acetate, ethylene-vinyl acetate copolymers (EVA) and ionomers.
  • Ethylene-vinyl acetate copolymers are typically used as encapsulants or sealants in the production of solar modules of crystalline silicon cells, cf.
  • WO 2006/095911 To attain the above-mentioned desirable mechanical properties of the solar modules, such as mechanical strength, adhesive strength as well as rigidity and solidity of the layers, that polymer is subjected to a cross-linking reaction.
  • Cross- linking is routinely carried out by using an organic peroxide initiator, which is a cross- linking agent of first choice.
  • organic peroxide initiator which is a cross- linking agent of first choice.
  • cross-linking not only significantly increases the time of lamination, but the initiator used generates volatile side products that forms bubbles and can cause homogeneity problem in encapsulants and thus efficiency loss in the modules.
  • the volatile compounds need to be removed by aspiration, which makes the lamination process more complicated.
  • thermoplastic polymers e.g. polyurethane
  • thermoplastic polymers can be used without cross-linking. Nevertheless, thermoplastic polymers have significant problems with stability, transparency, adhesion or electrical properties which render these products unsuitable as encapsulants.
  • JP 2000-186114 describes the use of thermoplastic copolymers of ethylene and unsaturated carboxylic acids with high molecular weight as encapsulants for solar cells. Nevertheless, films made of such copolymers have too high E-modulus and thus are very rigid at lower temperature. The lack of elasticity leads to mechanical failure and decreases the efficiency in the solar modules drastically. At the same time, the described polymers have low adhesion to glass and the solar cells and thus, the use of these copolymers would require extra additives.
  • unsaturated carboxylic acids of the type acrylic or methacrylic acid in selected ranges of the monomers with low viscosity can be used as encapsulating materials in laminates for solar cell modules because of their appropriate elasticity at low temperature.
  • These encapsulants showed excellent electrical and good other mechanical properties. Moreover, their adhesion to glass is superior compared to their high molecular weight analogs and their transparency is above the required minimum 90%.
  • the present invention relates to a solar cell module, which comprises a) A light transparent upper protective laminate exposable to solar radiation; b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
  • Ri and R 2 are identical or different.
  • Ri represents hydrogen or methyl
  • R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl
  • the dynamic melt viscosity of the polymer is in the range of 5 000 50 000, preferably 10 000 - 50 000, mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min., (190°C/2.16 kg) according to DIN 53735; and
  • the E-modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C bottom protective laminate according to ISO 6721 -1 ;
  • the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410;
  • a preferred embodiment of the invention relates to a solar cell module, which comprises
  • a light transparent upper protective laminate exposable to solar radiation b) One electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i and R 2 are as defined above; and
  • Another preferred embodiment relates to a solar cell module, which comprises
  • a light transparent upper protective laminate exposable to solar radiation b') A sequence of alternating electric energy generating laminates composed of solar cell elements and layers of polymer compositions of copolymers of ethylene and ethylenically unsaturated carboxylic acid (I), wherein R-i and R 2 are as defined above; and solar light permeable protective laminates; and
  • a solar cell also called photovoltaic cell or photoelectric cell
  • a solar cell is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect.
  • Assemblies of solar cells are used to make solar cell modules which are used to cap- ture energy from sunlight.
  • the resulting integrated group of modules all oriented in one plane is referred to in the solar industry as a solar panel.
  • the general public and some casual writers often refer to solar modules incorrectly as solar panels; technically this is not the correct usage of terminology. Nevertheless, both designations are seen in regular use, in reference to what are actually solar modules.
  • the distinction between a module and a panel is that a module cannot be disassembled into smaller re-usable components in the field, whereas a solar panel is assembled from, and can be disassembled back into a stack of solar modules.
  • the electrical energy generated from solar modules referred to as solar power, is an example of solar energy.
  • Photovoltaics is the field of technology and research related to the practical application of photovoltaic cells in producing electricity from light, though it is often used specifically to refer to the generation of electricity from sunlight.
  • a solar cell module is generally a package or assembly of layers or laminates comprising
  • the light transparent upper protective laminate a) is exposed to solar radiation and consists of transparent material, such as acrylic resins, polycarbonates, polyesters or fluorine-containing resins, preferably glass.
  • transparent material such as acrylic resins, polycarbonates, polyesters or fluorine-containing resins, preferably glass.
  • acrylic resins such as acrylic resins, polycarbonates, polyesters or fluorine-containing resins, preferably glass.
  • the electric energy generating laminate b) is composed of solar cell elements encapsulated within polymer compositions.
  • the solar cell elements are based on material, such as amorphous or crystalline silicon, cadmium-telluride, gallium arsenic, copper- indium-gallium selenide and copper-iridium-selenium, covered by laminates, such as foils or sheets, of suitable polymers, which is in the case of the present invention the copolymer of ethylene and an ethylenically unsaturated carboxylic acid of the formula (I).
  • laminates ensure the rigidity and stability of the solar cell module by en- suring sufficient light transparency and connecting the solar cell elements with the upper protective laminate a).
  • the laminates for the solar cell elements are usually applied in a thickness of about 0.1 - 1.2 mm, preferably 0.1 - 1.0 mm, and can be produced by known laminate forming methods, such as extrusion methods or calandering.
  • the solar light bottom protective laminate c) is located below the electric energy generating laminate b) and consists of a light-permeable or preferably light-impermeable layer, back-sheet, which may consist of a large variety of materials, such as polytetrafluoroethylene, polyethyleneterephtalate, polyvinylfluoride, polyamide, or their combination produced by cooextrusion, preferably polytetrafluoroethylene and polyamide, or materials from metal such as tin, aluminium, preferably electrically oxidised aluminum, steel and others.
  • the light transparent upper protective laminate a) is exposed to solar radiation; and b'), a sequence of alternating electric energy generating laminates is placed below the laminate a).
  • These laminates are composed of layers of solar cell elements, each encapsulated by light transparent layers of the polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I).
  • These electric energy generating laminates are placed above the solar light impermeable bottom protective laminate c).
  • the solar cell elements of the electric energy generating laminate b) are semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements.
  • Such solar cell elements are based on semiconductors of the type silicon, such as silicon in thick or thin layers, lll-V elements, such as Ga-As cells, ll-VI elements, such as Cd-Te cells, or l-lll-VI elements, such as CIS (copper-indium-disulphide) cells or CIGS (copper-indium-galium-diselenide) cells.
  • silicon such as silicon in thick or thin layers
  • lll-V elements such as Ga-As cells
  • ll-VI elements such as Cd-Te cells
  • l-lll-VI elements such as CIS (copper-indium-disulphide) cells or CIGS (copper-indium-galium-diselenide) cells.
  • the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R 2 represents hydrogen.
  • a particularly preferred embodiment of the invention refers to the solar cell module, wherein the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R 2 represents hydrogen.
  • the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R 2 represents hydrogen.
  • Copolymers of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein Ri and R 2 are identical or different; and Ri represents hydrogen or methyl; and R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl are known, belong to the group of ethylene copolymer waxes and commercially available, e.g. from BASF, Dupont, Dow or Honeywell.
  • R 2 defined as CrCi 0 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethyl- propyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylthexyl, n-nonyl or n-decyl, particularly methyl.
  • Preferred is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R 2 represents hydrogen.
  • a preferred embodiment relates to a solar cell module, which comprises
  • the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
  • melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735;
  • the E-modulus of the film made of the copolymer is in the range of 1.0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1.
  • a preferred embodiment relates to a solar cell module, which comprises b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
  • Suitable copolymers of ethylene and an ethylenically unsaturated carboxylic acid (I) comprise as co-monomers in copolymerizable form 5-30% methacrylic acid und 70- 95% ethylene (weight-%, based on the weight of the co-polymer).
  • the copolymer which has a dynamic melt viscosity in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min (190°C/2,16 kg) according to DIN 53735; and the E-modulus of the film made of the copolymer is in the range of 0,1 - 100.0 GPa, preferably 1 .0 -10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1 ; and wherein the transparency of the film is above 90% in the wave length of 350nm - 1 10Onm according to DIN EN 410;
  • the dynamic melt viscosity of the co-polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa-s (at 120°C), according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min (190°C/ 2.16 kg), according to DIN 53735;
  • the E-modulus of the film made of the co-polymer is in the range of 0.1 - 100.0, preferably 1 -10.0 MPa at 0°C, according to ISO 527-2 1 A; and
  • the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
  • the density of the copolymer is from 0,90 to 0,99, preferably from 0,94 to 0,98 g/cm 3 in accordance with DIN 53479.
  • copolymers are commercially available, e.g. from BASF, Dupont, Dow, or Honeywell, or can be produced by known methods, such as the ones described in U.S. Patent Application Publication No. 2006/0124554 A 1.
  • copolymers may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophos- phorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV-absorbers of the 2-hydroxy- benzophenone, 2-(2'-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)-1 ,3,5- triazine groups.
  • additives for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophos- phorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV-absorbers of the
  • Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles.
  • Preferred specific antioxidants include octade- cyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol- tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-di- tert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 31 14), 1 ,3,5-trimethyl-2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330), triethyleneglycol- bis[3-(3- tert-
  • Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphas- piro[5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl- 1 ,1 '-biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)- [1 ,1 -biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ).
  • Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1 -methyl-1-phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2- (2H-benzotriazole-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-ben- zotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol (TINUVIN 350), 2,2'-methylenebis(6- (2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6- diphenyl-1 ,3,5-triazin-2-yl
  • additives are optionally present in the co-polymers defined above in amounts from 0,1 to 2 wt.-%, based on the weight of the co-polymer.
  • a further embodiment of the invention refers to laminates composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 95.0 wt- % (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula Wherein
  • Ri and R 2 are identical or different.
  • Ri represents hydrogen or methyl
  • R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl
  • the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min. (190°C/2.16 kg) according to DIN 53735; and
  • the E-modulus of the film made of the copolymer is in the range of 0.1 - 100.0 GPa at 0°C bottom protective laminate according to ISO 6721 - 1 ;
  • the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
  • the solar cell elements are based on material, such as amorphous or crystalline silicon, cadmium-telluride, gallium arsenic, copper-indium-gallium selenide and copper-iridium-selenium and are covered by foils or sheets, of copolymers of ethylene and the ethylenically unsaturated carboxylic acid of the formula (I). These laminates ensure the rigidity and stability of the solar cell module by ensuring sufficient light transparency and connecting the solar cell elements with the upper protective laminate a).
  • the laminates for the solar cell elements are usually applied in a thickness of about 0.1 - 1.2 mm, preferably 0.1 - 1.0 mm, and can be produced by known laminate forming methods, such as extrusion methods or calandering.
  • the co-polymer of ethylene and the ethylenically unsaturated carboxylic acid (I) described above is applied to the semiconductor layer by lamination methods wherein a layer or film are applied the surface by known methods, such as film or sheet co-extrusion methods.
  • the co-polymer can be extruded in molten form and allowed to congeal on the semiconductor level.
  • the copolymers exhibit good adhesion to the upper and lower layers of the solar cell module.
  • a preferred embodiment of the invention refers to a laminate, which comprises
  • Ri represents hydrogen or methyl
  • R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl;
  • the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min (190°C/2.16 kg) according to DIN 53735;
  • the E-Modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C;
  • the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
  • melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735;
  • the E-modulus of the film made of the copolymer is in the range of 1 .0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1.
  • the dynamic melt viscosity of the copolymer in the laminate is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa-s (at 120°C), according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min (190°C/ 2.16 kg), according to DIN 53735;
  • the E-modulus of the film made of the co-polymer is in the range of 0.1 - 100.0, preferably 1 -10.0 MPa at 0°C, according to ISO 527-2 1 A; and
  • the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
  • the density of the copolymer is from 0,90 to 0,99, preferably from 0,94 to 0,98 g/cm 3 in accordance with DIN 53479.
  • a further embodiment of the invention relates to a laminate, which is composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
  • a laminate which is composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
  • a particularly preferred embodiment of the invention refers to a laminate, which comprises
  • a further embodiment refers to a process for the preparation of electric energy gene- rating laminates, which comprises encapsulating or covering by the methods described above semiconductors with layers of an uncross-linked polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I), wherein
  • Ri and R 2 are identical or different.
  • Ri represents hydrogen or methyl
  • R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl
  • the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min,
  • the E-modulus of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C;
  • the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
  • a preferred embodiment of the invention relates to the process, which comprises encapsulating semiconductors based on amorphous or partially or purely crystalline silicon within an uncross-linked copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R 2 represents hydrogen.
  • Ri and R 2 are identical or different; and Ri represents hydrogen or methyl;
  • R 2 represents hydrogen or straight chain or branched CrCi 0 alkyl
  • the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s, (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min,
  • the E-Modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C;
  • the transparency of the film is above 90% in the wave length of 350nm - 1 100nm according to DIN EN 410;
  • eth- ylene and methacrylic acid are copolymerized continuously in high pressure autoclave.
  • Ethylene (12.0 kg/h) is fed under 1700 to 2500 bar in the autoclave.
  • methacrylic acid (Table 1 ) is pressurized first to 260 bar and it was fed with another compressor under 1700 to 2500 bar in the autoclave.
  • tert.-amylperoxypivalate in isododecane (Table 1 ) is fed with another compressor under 1700 to 2500 bar in the autoclave.
  • Treactor is maximum temperature in the autoclave
  • MAS methacrylic acid
  • EMAS ethylene-methacrylic acid copolymer
  • PA propionaldehyde
  • ID isododecane (2,2,4,6,6-pentamethylheptane)
  • PO tert- amylperoxypivalate
  • c(PO) concentration of PO in ID in mol/l
  • the conversion of methacrylic acid is expected to be 100%.
  • EMAS in powder form is homogenously layered between two 200 x 200 mm polyester foils.
  • the foils were placed in a 200 x 200 x 0.45 mm press frame of a Wick- ert Press Type 29363.
  • the press is heated at 150°C, and the polymer pressurized with 150 bar for 10 min.
  • the press is cooled to room temperature within 10 min. After the cooling phase the film obtained with a dimension of 200 x200 x 0.45 mm is subjected to further analysis.
  • Adhesion is measured after lamination at 150°C for 1 min. with an applied pressure of 400 N/30cm 2 . Peel test is performed according to ASTM D903-98 in 180° with 5 differ- ent samples. An average value of the 5 measurements is weighed with the peak and average adhesion of the single measurement is shown in the table.
  • a film made of the EMAS 1 is placed on the top of a 200 x 200 x 0.5 mm foil made of polyvinylidene fluoride (Tedlar® SP, Dupont).
  • a silicon solar cell from crystalline silicone having a thickness of 2 mm and a 100 x 100 mm size is placed on top of the film of EMAS 1 , 50 mm from all 4 margins of the EMAS film.
  • a copper stripe as current collector is brazed on both sides of the cell so that they freely looked out of the layers.
  • the cell is covered with another film of EMAS and a glass plate is placed on the top with a size of 200X200X3 mm (Centrosol C from Centrosolar Glas).
  • the sandwich structure obtained is placed into a laminator equipped with heating and vacuum units (Spaleck-Stevens InnoTech GmbH).
  • the laminator is heated up to 40°C.
  • the temperature kept on 40°C and the atmosphere in the laminator is evacuated.
  • the temperature is raised to 120°C within 5 minutes and at 120°C nitrogen is led into the topside of the laminator to reach the ambient pressure, while the vacuum is kept on the bottom side of the films.
  • the laminator is cooled down after 1 minute, while nitrogen is led into the whole volume of the laminator.
  • the obtained module was free of mechanical defects and the bubbles between the glass and the encapsulant.

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Abstract

The invention relates to solar cell modules, laminates composed of solar cell elements encapsulated within a polymer composition of a co-polymer of ethylene and an ethylenically unsaturated carboxylic acid and compositions which comprise semiconductors selected from the group consisting of silicon, III-V, II-VI and I-III-VI elements.

Description

Ethylene-(meth)acrylic-acid-copolymers for solar cell laminates
Description The invention relates to solar cell modules, laminates composed of solar cell elements encapsulated within a polymer composition of a copolymer of ethylene and an ethyl- enically unsaturated carboxylic acid, compositions which comprise semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements; and a copolymer of ethylene and an ethylenically unsaturated carboxylic acid, a process for the preparation of electric energy generating laminates, and the use of an uncross- linked polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid for encapsulating semi-conductors.
Polymers are commonly used in the manufacture of modules comprising electronic devices, such as solar cells, also known as photo-voltaic cells, liquid crystal panels, electro-luminescent devices and plasma display units. These modules often comprise an electronic device in combination with one or more substrates, e.g. glass cover sheets, often positioned between two substrates in which one or both of the substrates comprise glass, metal, plastic, rubber or another material.
The polymers are typically used as encapsulants or sealants for the module or, depen- ding on the design of the module, as a skin layer component of the module, e.g. a back-skin in a solar cell module. Typical polymers include silicone resins, epoxy resins, polyvinyl butyral resins, cellulose acetate, ethylene-vinyl acetate copolymers (EVA) and ionomers.
U.S. Patent Application Publication No. 2001/0045229 A1 identifies a number of properties desirable in any polymeric material that is intended for use in the
construction of an electronic device module. These properties include
(i) protecting the device from exposure to external environmental effects, e.g.
moisture and air, particularly over long periods of time
(ii) protecting against mechanical shock effect
(iii) strong adhesion to the electronic device and substrates
(iv) facile processing, including sealing
(v) good transparency
(vi) short cure times with protection of the device from mechanical stress resulting from polymer shrinkage during cure
(vii) high electrical resistance with little, if any, electrical conductance and
(viii) low cost. There is urgent need for suitable polymer materials that delivers maximum performance of all of these properties in any particular application.
Ethylene-vinyl acetate copolymers (EVA) are typically used as encapsulants or sealants in the production of solar modules of crystalline silicon cells, cf.
WO 2006/095911. To attain the above-mentioned desirable mechanical properties of the solar modules, such as mechanical strength, adhesive strength as well as rigidity and solidity of the layers, that polymer is subjected to a cross-linking reaction. Cross- linking is routinely carried out by using an organic peroxide initiator, which is a cross- linking agent of first choice. However, cross-linking not only significantly increases the time of lamination, but the initiator used generates volatile side products that forms bubbles and can cause homogeneity problem in encapsulants and thus efficiency loss in the modules. To minimize this problem, the volatile compounds need to be removed by aspiration, which makes the lamination process more complicated.
As an alternative, thermoplastic polymers, e.g. polyurethane, can be used without cross-linking. Nevertheless, thermoplastic polymers have significant problems with stability, transparency, adhesion or electrical properties which render these products unsuitable as encapsulants.
JP 2000-186114 describes the use of thermoplastic copolymers of ethylene and unsaturated carboxylic acids with high molecular weight as encapsulants for solar cells. Nevertheless, films made of such copolymers have too high E-modulus and thus are very rigid at lower temperature. The lack of elasticity leads to mechanical failure and decreases the efficiency in the solar modules drastically. At the same time, the described polymers have low adhesion to glass and the solar cells and thus, the use of these copolymers would require extra additives.
It is a goal to find a suitable polymer material that can be used without cross-linking, has excellent electrical properties, high transparency, suitable mechanical properties and satisfactory elasticity at lower temperature.
It has surprisingly been found that copolymers of ethylene and ethylenically
unsaturated carboxylic acids of the type acrylic or methacrylic acid in selected ranges of the monomers with low viscosity can be used as encapsulating materials in laminates for solar cell modules because of their appropriate elasticity at low temperature. These encapsulants showed excellent electrical and good other mechanical properties. Moreover, their adhesion to glass is superior compared to their high molecular weight analogs and their transparency is above the required minimum 90%.
Therefore, the present invention relates to a solar cell module, which comprises a) A light transparent upper protective laminate exposable to solar radiation; b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
Figure imgf000004_0001
Wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and
Wherein the dynamic melt viscosity of the polymer is in the range of 5 000 50 000, preferably 10 000 - 50 000, mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min., (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C bottom protective laminate according to ISO 6721 -1 ; and
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410; and
c) A bottom protective laminate.
A preferred embodiment of the invention relates to a solar cell module, which comprises
a) A light transparent upper protective laminate exposable to solar radiation; b) One electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i and R2 are as defined above; and
c) A solar light impermeable bottom protective laminate.
Another preferred embodiment relates to a solar cell module, which comprises
a) A light transparent upper protective laminate exposable to solar radiation; b') A sequence of alternating electric energy generating laminates composed of solar cell elements and layers of polymer compositions of copolymers of ethylene and ethylenically unsaturated carboxylic acid (I), wherein R-i and R2 are as defined above; and solar light permeable protective laminates; and
c) A solar light impermeable bottom protective laminate.
A solar cell (also called photovoltaic cell or photoelectric cell) is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect.
Assemblies of solar cells are used to make solar cell modules which are used to cap- ture energy from sunlight. When multiple modules are assembled together (such as prior to installation on a pole-mounted tracker system), the resulting integrated group of modules all oriented in one plane is referred to in the solar industry as a solar panel. The general public and some casual writers often refer to solar modules incorrectly as solar panels; technically this is not the correct usage of terminology. Nevertheless, both designations are seen in regular use, in reference to what are actually solar modules. The distinction between a module and a panel is that a module cannot be disassembled into smaller re-usable components in the field, whereas a solar panel is assembled from, and can be disassembled back into a stack of solar modules. The electrical energy generated from solar modules, referred to as solar power, is an example of solar energy.
Photovoltaics is the field of technology and research related to the practical application of photovoltaic cells in producing electricity from light, though it is often used specifically to refer to the generation of electricity from sunlight.
A solar cell module is generally a package or assembly of layers or laminates comprising
a) A light transparent upper protective laminate exposed to solar radiation;
b) Electric energy generating laminates composed of solar cell elements
encapsulated within the above-defined polymer composition; and
c) A solar bottom protective laminate.
The light transparent upper protective laminate a) is exposed to solar radiation and consists of transparent material, such as acrylic resins, polycarbonates, polyesters or fluorine-containing resins, preferably glass. The function of this layer is self-evident.
The electric energy generating laminate b) is composed of solar cell elements encapsulated within polymer compositions. The solar cell elements are based on material, such as amorphous or crystalline silicon, cadmium-telluride, gallium arsenic, copper- indium-gallium selenide and copper-iridium-selenium, covered by laminates, such as foils or sheets, of suitable polymers, which is in the case of the present invention the copolymer of ethylene and an ethylenically unsaturated carboxylic acid of the formula (I). These laminates ensure the rigidity and stability of the solar cell module by en- suring sufficient light transparency and connecting the solar cell elements with the upper protective laminate a).
The laminates for the solar cell elements are usually applied in a thickness of about 0.1 - 1.2 mm, preferably 0.1 - 1.0 mm, and can be produced by known laminate forming methods, such as extrusion methods or calandering.
The solar light bottom protective laminate c) is located below the electric energy generating laminate b) and consists of a light-permeable or preferably light-impermeable layer, back-sheet, which may consist of a large variety of materials, such as polytetrafluoroethylene, polyethyleneterephtalate, polyvinylfluoride, polyamide, or their combination produced by cooextrusion, preferably polytetrafluoroethylene and polyamide, or materials from metal such as tin, aluminium, preferably electrically oxidised aluminum, steel and others.
Various arrangements of the above-mentioned layers are possible:
a) The light transparent upper protective laminate exposed to solar radiation; b) One electric energy generating laminate composed of solar cell elements encapsulated or covered by foils or sheets of the polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I); and
c) One solar light impermeable bottom protective laminate.
In the alternative, the light transparent upper protective laminate a) is exposed to solar radiation; and b'), a sequence of alternating electric energy generating laminates is placed below the laminate a). These laminates are composed of layers of solar cell elements, each encapsulated by light transparent layers of the polymer composition of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I). These electric energy generating laminates are placed above the solar light impermeable bottom protective laminate c).
The solar cell elements of the electric energy generating laminate b) are semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements.
Such solar cell elements are based on semiconductors of the type silicon, such as silicon in thick or thin layers, lll-V elements, such as Ga-As cells, ll-VI elements, such as Cd-Te cells, or l-lll-VI elements, such as CIS (copper-indium-disulphide) cells or CIGS (copper-indium-galium-diselenide) cells.
Preferred are silicon cells in thick layers based on mono-crystalline or poly-crystalline silicon or silicon cells in thin layers based on amorphous or crystalline silicon, particu- larly micro-crystalline silicon.
According to a preferred embodiment the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R2 represents hydrogen.
A particularly preferred embodiment of the invention refers to the solar cell module, wherein the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R2 represents hydrogen.
Copolymers of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein Ri and R2 are identical or different; and Ri represents hydrogen or methyl; and R2 represents hydrogen or straight chain or branched CrCi0alkyl are known, belong to the group of ethylene copolymer waxes and commercially available, e.g. from BASF, Dupont, Dow or Honeywell.
R2 defined as CrCi0alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethyl- propyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylthexyl, n-nonyl or n-decyl, particularly methyl.
Preferred is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R2 represents hydrogen.
A preferred embodiment relates to a solar cell module, which comprises
b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer (I),
Wherein the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
Wherein the melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 1.0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1.
A preferred embodiment relates to a solar cell module, which comprises b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
Suitable copolymers of ethylene and an ethylenically unsaturated carboxylic acid (I) comprise as co-monomers in copolymerizable form 5-30% methacrylic acid und 70- 95% ethylene (weight-%, based on the weight of the co-polymer). It has been found that the copolymer which has a dynamic melt viscosity in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min (190°C/2,16 kg) according to DIN 53735; and the E-modulus of the film made of the copolymer is in the range of 0,1 - 100.0 GPa, preferably 1 .0 -10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1 ; and wherein the transparency of the film is above 90% in the wave length of 350nm - 1 10Onm according to DIN EN 410;
is suitable as encapsulant material for the preparation of the solar cell modules as described above.
According to an alternative embodiment, the dynamic melt viscosity of the co-polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa-s (at 120°C), according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min (190°C/ 2.16 kg), according to DIN 53735;
The E-modulus of the film made of the co-polymer is in the range of 0.1 - 100.0, preferably 1 -10.0 MPa at 0°C, according to ISO 527-2 1 A; and
The transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
The density of the copolymer is from 0,90 to 0,99, preferably from 0,94 to 0,98 g/cm3 in accordance with DIN 53479.
Such copolymers are commercially available, e.g. from BASF, Dupont, Dow, or Honeywell, or can be produced by known methods, such as the ones described in U.S. Patent Application Publication No. 2006/0124554 A 1.
These copolymers may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophos- phorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV-absorbers of the 2-hydroxy- benzophenone, 2-(2'-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)-1 ,3,5- triazine groups.
Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles. Preferred specific antioxidants include octade- cyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol- tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-di- tert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 31 14), 1 ,3,5-trimethyl-2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330), triethyleneglycol- bis[3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionate] (IRGANOX 245), and Ν,Ν'- hexane-1 ,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (IRGANOX 1098). Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphas- piro[5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl- 1 ,1 '-biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)- [1 ,1 -biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ). Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1 -methyl-1-phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2- (2H-benzotriazole-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-ben- zotriazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol (TINUVIN 350), 2,2'-methylenebis(6- (2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6- diphenyl-1 ,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (TINUVIN 1577), 2-(2'-hydroxy-5'- methylphenyl)benzotriazole (TINUVIN P), 2-hydroxy-4-(octyloxy)benzophenone (CHI- MASSORB 81 ), 1 ,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{[(2'-cyano- 3',3'- diphenylacryloyl)oxy]methyl}-propane (UVINUL 3030, BASF), ethyl-2-cyano-3,3-di- phenylacrylate (UVINUL 3035, BASF), and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL 3039, BASF).
These additives are optionally present in the co-polymers defined above in amounts from 0,1 to 2 wt.-%, based on the weight of the co-polymer.
A further embodiment of the invention refers to laminates composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 95.0 wt- % (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
Figure imgf000009_0001
Wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and
Wherein the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min. (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 0.1 - 100.0 GPa at 0°C bottom protective laminate according to ISO 6721 - 1 ; and
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
The solar cell elements are based on material, such as amorphous or crystalline silicon, cadmium-telluride, gallium arsenic, copper-indium-gallium selenide and copper-iridium-selenium and are covered by foils or sheets, of copolymers of ethylene and the ethylenically unsaturated carboxylic acid of the formula (I). These laminates ensure the rigidity and stability of the solar cell module by ensuring sufficient light transparency and connecting the solar cell elements with the upper protective laminate a).
The laminates for the solar cell elements are usually applied in a thickness of about 0.1 - 1.2 mm, preferably 0.1 - 1.0 mm, and can be produced by known laminate forming methods, such as extrusion methods or calandering.
Typically, the co-polymer of ethylene and the ethylenically unsaturated carboxylic acid (I) described above is applied to the semiconductor layer by lamination methods wherein a layer or film are applied the surface by known methods, such as film or sheet co-extrusion methods. In an alternative embodiment, the co-polymer can be extruded in molten form and allowed to congeal on the semiconductor level. The copolymers exhibit good adhesion to the upper and lower layers of the solar cell module.
A preferred embodiment of the invention refers to a laminate, which comprises
a) Semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements; and β) A copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid(l), wherein Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min (190°C/2.16 kg) according to DIN 53735;
Wherein the E-Modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C; and
Wherein the transparency of the film is above 90% in the wave length of
350nm - 1 100nm according to DIN EN 410.
A further embodiment refers to a laminate, which is composed of solar cell elements encapsulated within a polymer composition of a copolymer (I),
Wherein the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
Wherein the melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 1 .0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1. According to an alternative embodiment, the the dynamic melt viscosity of the copolymer in the laminate is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa-s (at 120°C), according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min., preferably higher than 200 g/min (190°C/ 2.16 kg), according to DIN 53735;
The E-modulus of the film made of the co-polymer is in the range of 0.1 - 100.0, preferably 1 -10.0 MPa at 0°C, according to ISO 527-2 1 A; and
The transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
The density of the copolymer is from 0,90 to 0,99, preferably from 0,94 to 0,98 g/cm3 in accordance with DIN 53479.
A further embodiment of the invention relates to a laminate, which is composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
A particularly preferred embodiment of the invention refers to a laminate, which comprises
a) A semiconductor based on amorphous or partially or purely crystalline
silicon; and
β) A copolymer of ethylene and an ethylenically unsaturated carboxylic
acid (I), wherein R-i represents methyl and R2 represents hydrogen.
A further embodiment refers to a process for the preparation of electric energy gene- rating laminates, which comprises encapsulating or covering by the methods described above semiconductors with layers of an uncross-linked polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I), wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl;
The dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000, mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min,
(190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C;
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
A preferred embodiment of the invention relates to the process, which comprises encapsulating semiconductors based on amorphous or partially or purely crystalline silicon within an uncross-linked copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R2 represents hydrogen.
The use of an uncross-linked polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer), particularly 70.0 -84.0 wt.-% ethylene, and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer), particularly 16.0 - 30.0 wt.-% of an ethylenically unsaturated carboxylic acid (I), wherein
Ri and R2 are identical or different; and Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and
The dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000, preferably 10 000 - 50 000 mPa.s, (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100, preferably higher than 200 g/min,
(190°C/2.16 kg) according to DIN 53735; and
Wherein the E-Modul of the film made of the copolymer is in the range of 0,1 - 100 GPa, preferably 1 -10 GPa at 0°C;
Wherein the transparency of the film is above 90% in the wave length of 350nm - 1 100nm according to DIN EN 410;
for encapsulating semi-conductors; and particularly the use of an uncross-linked copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein R-i represents methyl and R2 represents hydrogen, for encapsulating semiconductors based on amorphous or partially or purely crystalline silicon is also subject matter of the present invention.
The following Examples illustrate the Invention:
A) Materials and Methods
Synthesis of Copolymers
As described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), eth- ylene and methacrylic acid are copolymerized continuously in high pressure autoclave. Ethylene (12.0 kg/h) is fed under 1700 to 2500 bar in the autoclave. Separately, methacrylic acid (Table 1 ) is pressurized first to 260 bar and it was fed with another compressor under 1700 to 2500 bar in the autoclave. Separately, tert.-amylperoxypivalate in isododecane (Table 1 ) is fed with another compressor under 1700 to 2500 bar in the autoclave. Separately, propionaldehyde in isododecane (Table 1 ) is pressurized first to 260 bar and fed continuously with another compressor under 1700 to 2500 bar in the autoclave. The temperature in autoclave is held between 220 and 240°C. The properties of the collected copolymers are summarized in Table 2. Table 1 : Conditions for polymerisation
Figure imgf000014_0001
Treactor is maximum temperature in the autoclave
Abbreviations: MAS: methacrylic acid, EMAS: ethylene-methacrylic acid copolymer, PA: propionaldehyde, ID: isododecane (2,2,4,6,6-pentamethylheptane), PO: tert- amylperoxypivalate, c(PO): concentration of PO in ID in mol/l
The conversion of methacrylic acid is expected to be 100%.
Table 2: Analytic data of the copolymers
Figure imgf000014_0002
η: dynamic melt viscosity, measured at 120°C in a cone and plate viscometer (PP 35 Ti) 1 .0 mm column, D = 10 [1/s] according to DIN 53018-1 ; melt flow index (190°C/ 2.16 kg) measured according to ISO 527-2 1 A; the content of MAS is calculated from measurement of the acid number by titration with tetrabutylammoniumhydroxide (0.1 mol/l in xylene); the content of ethylene is calculated as 100%-content of MAS.
B) Production of encapsulant film from ethylene-methacrylic acid film
12.0 g EMAS in powder form is homogenously layered between two 200 x 200 mm polyester foils. The foils were placed in a 200 x 200 x 0.45 mm press frame of a Wick- ert Press Type 29363. The press is heated at 150°C, and the polymer pressurized with 150 bar for 10 min. The press is cooled to room temperature within 10 min. After the cooling phase the film obtained with a dimension of 200 x200 x 0.45 mm is subjected to further analysis.
Table 3: General Properties of Films
Figure imgf000015_0001
Table 4: Mechanical Properties of Films
Figure imgf000015_0002
Table 5: Electrical Properties of Films
Figure imgf000015_0003
Table 6: Transmittance and Adhesion of Films
Figure imgf000015_0004
Adhesion is measured after lamination at 150°C for 1 min. with an applied pressure of 400 N/30cm2. Peel test is performed according to ASTM D903-98 in 180° with 5 differ- ent samples. An average value of the 5 measurements is weighed with the peak and average adhesion of the single measurement is shown in the table.
C) Production of solar module from ethylene-methacrylic acid film
A film made of the EMAS 1 is placed on the top of a 200 x 200 x 0.5 mm foil made of polyvinylidene fluoride (Tedlar® SP, Dupont). A silicon solar cell from crystalline silicone having a thickness of 2 mm and a 100 x 100 mm size is placed on top of the film of EMAS 1 , 50 mm from all 4 margins of the EMAS film. A copper stripe as current collector is brazed on both sides of the cell so that they freely looked out of the layers. The cell is covered with another film of EMAS and a glass plate is placed on the top with a size of 200X200X3 mm (Centrosol C from Centrosolar Glas). The sandwich structure obtained is placed into a laminator equipped with heating and vacuum units (Spaleck-Stevens InnoTech GmbH). The laminator is heated up to 40°C. The temperature kept on 40°C and the atmosphere in the laminator is evacuated. The temperature is raised to 120°C within 5 minutes and at 120°C nitrogen is led into the topside of the laminator to reach the ambient pressure, while the vacuum is kept on the bottom side of the films. The laminator is cooled down after 1 minute, while nitrogen is led into the whole volume of the laminator. The obtained module was free of mechanical defects and the bubbles between the glass and the encapsulant.

Claims

Claims
1. A solar cell module, which comprises
a) A light transparent upper protective laminate exposable to solar radiation; b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
Figure imgf000017_0001
Wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and
Wherein the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min. (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 0.1 - 100.0 GPa at 0°C bottom protective laminate according to ISO 6721- 1 ; and
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410; and
c) A bottom protective laminate.
A solar cell module according to claim 1 , which comprises
b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer (I),
Wherein the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
Wherein the melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 1.0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721-1. A solar cell module according to claim 1 , which comprises b) At least one electric energy generating laminate composed of solar cell elements encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
4. A solar cell module according to claim 1 , which comprises
a) A light transparent upper protective laminate exposable to solar radiation; b') A sequence of alternating electric energy generating laminates composed of solar cell elements and layers of polymer compositions of copolymers of ethylene and ethylenically unsaturated carboxylic acids (I), wherein R-i and R2 are as defined as in claim 1 ; and
c) A solar light impermeable bottom protective laminate.
5. A solar cell module according to claim 1 , wherein the solar cell elements of the electric energy generating laminate b) are semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements.
6. A solar cell module according to claim 1 , wherein the polymer composition of the electric energy generating laminate b) comprises a copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein
Ri represents methyl and R2 represents hydrogen.
7. Laminates composed of solar cell elements encapsulated within a polymer
composition of a copolymer of 70.0 - 95.0 wt.-% (based on the weight of the copolymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
Figure imgf000018_0001
Wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and Wherein the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min. (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 0.1 - 100.0 GPa at 0°C bottom protective laminate according to ISO 6721 -
1 ; and
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
8. A laminate according to claim 7, which is composed of solar cell elements
encapsulated within a polymer composition of a copolymer (I),
Wherein the dynamic melt viscosity of the polymer is in the range of 10 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or
Wherein the melt flow index is higher than 200 g/min (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of
1 .0 - 10.0 GPa at 0°C bottom protective laminate according to ISO 6721 -1.
9. A laminate according to claim 7, which is composed of solar cell elements
encapsulated within a polymer composition of a copolymer of 70.0 - 84.0 wt.-% (based on the weight of the co-polymer) ethylene and 16.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid (I).
10. A laminate according to claim 7, which comprises
a) Semiconductors selected from the group consisting of silicon, lll-V, ll-VI and l-lll-VI elements; and
β) A copolymer of ethylene and an ethylenically unsaturated carboxylic
acid (I), wherein
Ri represents methyl and R2 represents hydrogen.
1 1 . A laminate according to claim 7, which comprises
a) A semiconductor based on amorphous or partially or purely crystalline
silicon; and
β) A copolymer of ethylene and an ethylenically unsaturated carboxylic
acid (I), wherein
Ri represents methyl and R2 represents hydrogen.
12. The use of a laminate according to claim 7 for the preparation of solar cell modules.
13. A process for the preparation of electric energy generating laminates, which
comprises encapsulating semiconductors within an uncross-linked polymer composition of 70.0 - 95.0 wt.-% (based on the weight of the co-polymer) ethylene and 5.0 - 30.0 wt.-% (based on the weight of the co-polymer) of an ethylenically unsaturated carboxylic acid of the formula
Figure imgf000020_0001
Wherein
Ri and R2 are identical or different; and
Ri represents hydrogen or methyl; and
R2 represents hydrogen or straight chain or branched CrCi0alkyl; and
Wherein the dynamic melt viscosity of the polymer is in the range of 5 000 - 50 000 mPa.s (at 120°C) according to DIN 53018-1 ; or the melt flow index is higher than 100 g/min. (190°C/2.16 kg) according to DIN 53735; and
Wherein the E-modulus of the film made of the copolymer is in the range of 0.1 - 100.0 GPa at 0°C bottom protective laminate according to ISO 6721 - 1 ; and
Wherein the transparency of the film is above 90% in the wave length of 350 nm - 1 100 nm according to DIN EN 410.
14. A process according to claim 13, which comprises encapsulating semiconductors based on amorphous or partially or purely crystalline silicon within an uncross- linked copolymer of ethylene and an ethylenically unsaturated carboxylic acid (I), wherein Ri represents methyl and R2 represents hydrogen.
PCT/EP2013/050843 2012-01-19 2013-01-17 Ethylene-(meth)acrylic-acid-copolymers for solar cell laminates WO2013107818A1 (en)

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