WO2010091925A1 - Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques - Google Patents

Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques Download PDF

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Publication number
WO2010091925A1
WO2010091925A1 PCT/EP2010/050702 EP2010050702W WO2010091925A1 WO 2010091925 A1 WO2010091925 A1 WO 2010091925A1 EP 2010050702 W EP2010050702 W EP 2010050702W WO 2010091925 A1 WO2010091925 A1 WO 2010091925A1
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WO
WIPO (PCT)
Prior art keywords
plastic
meth
acrylate
plastic molding
colored
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/EP2010/050702
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German (de)
English (en)
Inventor
Hans Lichtenstein
Claudius Neumann
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication of WO2010091925A1 publication Critical patent/WO2010091925A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/331—Coatings for devices having potential barriers for filtering or shielding light, e.g. multicolour filters for photodetectors
    • H10F77/337—Coatings for devices having potential barriers for filtering or shielding light, e.g. multicolour filters for photodetectors using interference filters, e.g. multilayer dielectric filters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • 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
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • 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
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/45—Wavelength conversion means, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • 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
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/496—Luminescent members, e.g. fluorescent sheets
    • 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
    • Y02E10/52—PV systems with concentrators

Definitions

  • the invention relates to a combination of fluorescence conversion dyes in plastic moldings of polymethyl (nneth) acrylate, which are used to convert the natural solar radiation in usable for the solar cell light.
  • the plastic moldings are polymehsiert by casting.
  • Photovoltaic cells can only partially convert the incident sunlight into usable electrical energy, a large part of the energy is lost in the form of heat.
  • a silicon solar cell can absorb all photons that have an energy above the band edge of 1.1 eV of the crystalline silicon. This corresponds to a wavelength ⁇ 1100 nm. The excess energy of the absorbed photons is converted into heat and leads to a heating of the photocell, the efficiency of the photocell is lowered.
  • WO 2007/031446 (BASF AG) describes fluorescence conversion solar cells composed of one or more glass plates or polymer plates which are coated with a fluorescent dye.
  • a fluorescent dye dyes based on Terrylencarbonklahvaten or combinations of these dyes with used other fluorescent dyes.
  • the disadvantage here is the separately required step of coating the glass plates with the formulation containing the dye.
  • Optical systems based on lenses or mirrors for the concentration of light on the solar cells are known, concentration factors of up to 1,000 times are achieved.
  • a disadvantage of the optical solutions is that the entire electromagnetic spectrum of the light is concentrated, so that not only the effective light is concentrated, but also the photovoltaic ineffective light. This leads to an undesirable thermal load on the solar cells and a reduction in the efficiency. In order not to let the temperatures get too high, you can actively or passively cool the solar cells.
  • the lenses or the lens systems must be tracked consuming mechanically the position of the sun, they also can only reflect the directly incident light. Diffused light contributes little or no energy. (see US Patent 5,489,297)
  • the solution further comprises the solution of the dyes or the dye mixtures in a monomer mixture, which is then polymerized to a plastic molding.
  • the plastic mold body can be constructed in one or more layers and include layers containing the same or different dyes or dye mixtures.
  • the individual layers may e.g. be firmly bonded by gluing or by polymerization. This can e.g. by methods described in applications DE 10233684 and DE 10254276.
  • the layering can also be done by loose stacking of the individual plastic moldings.
  • the solution according to the invention offers the following advantages:
  • the irradiated sunlight is converted into optimal wavelengths for silicon photovoltaic cells,
  • the preparation of the fluorescence conversion solar cells can be carried out by known methods,
  • the plastic molding is easily adaptable to the geometric and static requirements of the solar cell
  • the plastic molding is lighter than a comparable arrangement of mineral glass
  • the plastic molding can be equipped impact resistant, so that the solar cell array is protected against hail.
  • a particularly preferred group of monomers are (meth) acrylates
  • Expression (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
  • (Meth) acrylates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, butoxymethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, tetrahydrofurfuryl (meth ) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as o
  • sulfur-containing methacrylates such as, for example, ethylsulfinylethyl (meth)
  • These monomers may be used singly or as a mixture.
  • mixtures are particularly preferred which contain methacrylates and acrylic esters.
  • the polymerization is generally started with known free-radical initiators.
  • the preferred initiators include the well-known in the art azo initiators such as AIBN and IJ -Azobiscyclohexancarbonitril, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone, Dilaurylperoxyd, tert-butyl per-2-ethylhexanoat, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert Butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexan
  • Preferred impact-resistant castings which can be used to produce the polymethyl methacrylate molded body comprise 1% by weight to 30% by weight, preferably 2% by weight to 20% by weight, particularly preferably 3% by weight to 15% by weight %, in particular 5% by weight to 12% by weight, of an impact modifier which constitutes an elastomer phase of crosslinked polymer particles.
  • the impact modifier can be obtained in a manner known per se by bead polymerisation or by emulsion polymerisation.
  • Preferred impact modifiers are crosslinked particles having an average particle size in the range of 50 to 1,000 nm, preferably 60 to 500 nm and particularly preferably 80 to 120 nm.
  • Such particles can be obtained, for example, by the radical polymerization of mixtures which are generally at least 40% by weight, preferably 50% by weight to 70% by weight, of methyl methacrylate, 20% by weight to 80% by weight, preferably 25 wt .-% to 35 wt .-% butyl acrylate and 0.1 wt .-% to 2 wt .-%, preferably 0.5 wt .-% to 1 wt .-% of a crosslinking monomer, eg. B. a polyfunctional (meth) acrylate, such as.
  • a crosslinking monomer eg. B.
  • a polyfunctional (meth) acrylate such as.
  • allyl methacrylate and comonomers that can be copolymerized with the aforementioned vinyl compounds.
  • C 1 -C 4 -alkyl (meth) acrylates such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinylically polymerizable monomers, such as e.g. Styrene.
  • the mixtures for the preparation of the aforementioned particles may preferably comprise 0 wt .-% to 10 wt .-%, preferably 0.5 wt .-% to 5 wt .-% comonomers.
  • Particularly preferred toughening modifiers are polymerizate particles which have a two-layer, particularly preferably a three-layer core-shell structure.
  • core-shell polymers are described inter alia in EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 and EP-A 0 683 028.
  • Particularly preferred impact modifiers based on acrylate rubber have, inter alia, the following structure:
  • Core polymer with a methyl methacrylate content of at least 90
  • Wt .-% based on the weight of the core.
  • Shell 1 polymer having a butyl acrylate content of at least 80% by weight, based on the weight of the first shell.
  • Shell 2 polymer having a methyl methacrylate content of at least 90% by weight, based on the weight of the second shell.
  • the core and the shells may each contain other monomers in addition to the monomers mentioned. These have been previously set forth, with particularly preferred comonomers having a crosslinking effect.
  • a preferred acrylate rubber modifier may have the following structure:
  • the ratio of core to shell (s) of the acrylate rubber modifier can vary within wide limits.
  • the weight ratio of core to shell K / S is in the range from 20:80 to 80:20, preferably from 30:70 to 70:30 for modifiers with one shell or the ratio of core to shell 1 to shell 2 K / S1 / S2 in the range of 10:80:10 to 40:20:40, especially preferred from 20:60:20 to 30:40:30 for modifiers with two bowls.
  • the particle size of the core-shell modifier is usually in the range of 50 to 1000 nm, preferably 100 to 500 nm and more preferably from 150 to 450 nm, without this being a restriction.
  • the polymethyl (meth) acrylate molded body has an E-modulus of at least 2,800 N / mm 2 , preferably at least 3,300 N / mm 2 according to ISO 527/2.
  • the plastics molding may also be made of polycarbonate (PC), polystyrene (PS), polyamide (PA), polyester (PE), thermoplastic polyurethane (PU), polyethersulfone, polysulfones, vinyl polymers such as polyvinyl chloride (PVC).
  • PC polycarbonate
  • PS polystyrene
  • PA polyamide
  • PE polyester
  • PU polyethersulfone
  • polysulfones polysulfones
  • vinyl polymers such as polyvinyl chloride (PVC).
  • UV-A and / or UV-B absorbers are used as a light stabilizer UV-A and / or UV-B absorbers.
  • classes of substances which can be used are the HALS compounds.
  • HALS compounds are understood as meaning sterically hindered amines, as described, for example, in JP 0347856. This "hindered amine light stabilizers" catch the radicals from that form when radiation exposure. In the trade these products are brought 622 by Ciba under the trade name TINUVIN ® 123, Tinuvin ® 571, Tinuvin ® 770 and Tinuvin ®.
  • light stabilizers based on benzophenone derivatives can be used. These products are marketed by BASF under the brand UVINUL ® 5411. Benzotriazole based light stabilizers can also be used. In the trade, these products are made by Cytec under the brand CYASORB ® UV 5411 or Ciba under the trade name TINUVIN ® P, Tinuvin ® 571 and Tinuvin ® 234th
  • antioxidants sterically hindered phenols or phosphites or phosphonites can be used. In the trade, these products are made by Ciba under the trademarks Irganox ® and Irgafos ®.
  • suitable (meth) acrylic mixtures are placed in a mold and polymerized.
  • Such (meth) acrylic mixtures generally have the above-described (meth) acrylates, in particular methyl methacrylate.
  • the (meth) acrylic mixtures may contain the copolymers described above and, in particular for adjusting the viscosity, polymers, in particular poly (meth) acrylates.
  • the weight average molecular weight M w of the polymers prepared by cast-chamber processes is generally higher than the molecular weight of polymers used in molding compositions. This results in a number of known advantages. In general, the weight average molecular weight of polymers prepared by cast chamber processes is in the range of 500,000 to
  • photoconductive layers of the present invention can be produced by casting.
  • suitable acrylic resin mixtures are placed in a mold and polymerized.
  • a suitable acrylic resin includes, for example
  • the acrylic resin has the initiators necessary for the polymerization.
  • the components 1 to 4 and the initiators correspond to the compounds which are also used for the preparation of suitable polymethyl methacrylate molding compositions.
  • Gußsch For curing you can z.
  • Gußsch see, for example, DE 25 44 245, EP-B 570 782 or EP-A 656 548, apply, in which the polymerization of a plastic disc between two glass plates, which are sealed with a circulating string.
  • Preferred plastic substrates can be obtained from Evonik commercially under the trade name PLEXIGLAS ® GS.
  • the dimensions of the plastic substrates are for example (length X width X thickness) between 2 m length, 3 m width and the thickness can be between 1, 5 mm to 200 mm, preferably plates with the thickness range between 2 mm and 20 mm, particularly preferred are plates in the thickness range of 3 mm to 10 mm.
  • dyes dyes of the types perylene, terrylene and rylene derivatives can be prepared from the Lumogen ® - BASF, rhodamines, LDS ® row - number of exciton, substituted pyrans (such as DCM), coumarins (for example, Coumarin 30, Coumarin 1, Coumahn 102 etc.) oxazines (eg Nile Blue or also called Nile Blue A), pyridines, styryl derivatives, dioxazines, naphthalimides, thiazines, stilbenes and cyanines (eg DODCI) of e.g. B. Lambdachronne ® and Exciton ® are used.
  • the types of perylene, terrylene and rylene derivatives dyes are described in WO 2007/031446.
  • quantum dots e.g. based on cadmium selenide, cadmium sulfide, zinc sulfide, lead selenide, lead sulfide and the like. are suitable for it. Production and use of the Quantum Dots are described in US 2007/0132052, US 2007/0174939, WO 0229140, WO 2004022637, WO 2006065054 and WO 2007073467.
  • the photonic layer is arranged on the plastic molding, so that the sunlight must first penetrate this layer before the fluorescent dyes in the plastic molding can be excited to fluoresce
  • Interference filter stack filter, rugate filter, notch filter, etc.
  • notch filter e.g.
  • These are e.g. by depositing a plurality of thin dielectric layers having different refractive indices onto a substrate, (see Olaf Stenzel, "The Physics of Thin Film Optical Spectra", Springer-Verlag) and (N.Kaiser, HK Pulker, Optical Interference Coatings ", Springer-Verlag). Publishing company).
  • the layer thickness of the individual layer is generally smaller than the wavelength of light.
  • a further possibility is the use of photonic crystals which are described in the following applications (DE 10024466, DE 10204338, DE 10227071, DE 10228228, DE 102004055303, US Pat. No. 6,863,847, WO 0244301, DE 10357681, DE 102004009569, DE 102004032120, WO 2006045567, DE 10245848, DE 102006017163)
  • the individual spherical or hollow-spherical structures have the diameter of about 1/3 of the wavelength of light to be reflected (depending on the angle of incidence of the light and the distance of the balls).
  • an optically reflecting shaped body e.g. a mirror or a white foil or a plate.
  • the solar cell can be constructed of the usual materials, such as
  • c-Si Monocrystalline silicon
  • mc-Si multicrystalline silicon
  • a-Si amorphous silicon
  • Gallium arsenide GaAs
  • gallium indium phosphide GaInP
  • gallium indium arsenide GaInAs
  • gallium indium arsenic phosphide GaInAsP
  • gallium indium phosphide GaInP
  • gallium antimonide GaSb
  • tandem cells of gallium indium phosphide and gallium arsenide, of gallium indium arsenide and gallium indium arsenic phosphide, of gallium indium phosphide and gallium indium arsenide, of gallium arsenide and gallium antimonide or of gallium Arsenide and germanium or triple cells (triple solar cell) made of gallium indium phosphide, gallium arsenide and germanium or of gallium indium phosphide, gallium indium arsenide and gallium antimonide Il Vl semiconductor solar cells
  • Cadmium telluride CdTe
  • CdS cadmium sulfide
  • CIS cells copper indium diselenide (CulnSe2) or copper indium disulfide
  • CIGS cells copper indium gallium diselenide (CulnGaSe2)
  • the specified wavelength corresponds to the wavelength of the light which provides the energy equal to the energy of the energy gap of the semiconductor, ie with this light, the semiconductor works most effectively as a solar cell (the fluorescence conversion cell is tuned to this wavelength).
  • Example 1 Preparation of a homogeneously colored plate
  • Lumogen Yellow 083 0.15 part by weight Lumogen Yellow 083 (BASF) 0.16 part by weight Lumogen Orange 240 (BASF) 0.40 part by weight Lumogen Red 305 (BASF)
  • the final polymerization is carried out in a Temper Appendix Appendix at 115 ° C for about 4
  • Example 2 Device with three layers
  • the mixture is stirred vigorously, filled into a silicate glass chamber which is distanced with 3 mm thick cord and polymerized in a water bath at 45 ° C. for about 16 hours.
  • the final polymerization is carried out in a tempering at 115 ° C for about 4 hours.
  • the mixture is stirred vigorously, filled into a silicate glass chamber which is distanced with 3 mm thick cord and polymerized in a water bath at 45 ° C. for about 16 hours.
  • the final polymerization is carried out in a tempering at 115 ° C for about 4 hours.
  • the batch is stirred vigorously, filled into a 3mm thick cord spaced compartment formed of the green and red covers, and polymerized in the water bath at 45 ° C for about 16 hours.
  • the final polymerization is carried out in a tempering at 115 ° C for about 4 hours.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne une combinaison de colorants de conversion de fluorescence à base de polyméthyl(méth)acrylate, qui sont utilisés pour convertir le rayonnement naturel du soleil en une lumière utilisable pour les cellules solaires. Les corps formés en matière synthétique sont polymérisés dans le procédé de coulée.
PCT/EP2010/050702 2009-02-12 2010-01-22 Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques Ceased WO2010091925A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009000813A DE102009000813A1 (de) 2009-02-12 2009-02-12 Fluoreszenzkonversionssolarzelle I Herstellung im Plattengußverfahren
DE102009000813.6 2009-02-12

Publications (1)

Publication Number Publication Date
WO2010091925A1 true WO2010091925A1 (fr) 2010-08-19

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PCT/EP2010/050702 Ceased WO2010091925A1 (fr) 2009-02-12 2010-01-22 Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques

Country Status (3)

Country Link
DE (1) DE102009000813A1 (fr)
TW (1) TW201043681A (fr)
WO (1) WO2010091925A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012013455A1 (fr) * 2010-07-30 2012-02-02 Evonik Röhm Gmbh Pièce moulée en polyméthyl(meth)acrylate pour la conversion par fluorescence, leur fabrication par le procédé de coulée en plaque et leur utilisation dans des collecteurs solaires
US20220122781A1 (en) * 2018-08-17 2022-04-21 Eni S.P.A. Photovoltaic devices comprising luminescent solar concentrators and perovskite-based photovoltaic cells

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2008837C2 (en) * 2012-05-16 2013-11-20 Novopolymers N V Solar panel.

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