EP2873099A1 - Revetement optiquement actif pour l'amelioration du rendement de conversion photosolaire - Google Patents
Revetement optiquement actif pour l'amelioration du rendement de conversion photosolaireInfo
- Publication number
- EP2873099A1 EP2873099A1 EP13744756.1A EP13744756A EP2873099A1 EP 2873099 A1 EP2873099 A1 EP 2873099A1 EP 13744756 A EP13744756 A EP 13744756A EP 2873099 A1 EP2873099 A1 EP 2873099A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- optically active
- concentration
- matrix
- wavelength
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0232—Optical elements or arrangements associated with the device
- H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
-
- 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
- Optically active coating for improving photosolar conversion efficiency
- the present invention relates to the field of photosolar conversion, and more precisely 1 optimization of this conversion to improve the photoconversion efficiency of films or plates interposed between the solar radiation and equipment such as a greenhouse, a phytoreactor or a photovoltaic cell.
- It relates more particularly to the implementation of a doped interface with optically active constituents forming a light cascade.
- the term "light cascade” will be understood to mean the wavelength transfer occurring by the combination of a series of optically active constituents chosen so that the wavelength of re-emission of one type of constituent corresponds to the absorption wavelength of another type of constituent, each of the constituent types being defined by a retransmission wavelength different from the absorption wavelength.
- These constituents are of the photoluminescent type, scintillators, fluorescent, or laser dyes.
- the "light cascade" within the meaning of this patent may also incorporate one or more molecules producing an anti-Stokes displacement (the atom of the molecule thus emits a photon of energy equal to the sum of the energy of the absorbed photon and phonon, so the wavelength of the emitted photon is shorter).
- an anti-Stokes displacement the atom of the molecule thus emits a photon of energy equal to the sum of the energy of the absorbed photon and phonon, so the wavelength of the emitted photon is shorter.
- Stokes displacement is the difference in energy between the exciter wavelength and that, which is greater, therefore, of smaller energy than the emitted light.
- the molecule thus conserving an excess of energy which can be the source of the emission of a longer wavelength than that received (with a second photon). Displacement to smaller wavelengths (hence higher energy) than incident light may occur. Such a displacement is called anti-Stokes.
- the matrix present on the input surface a dichroic filter substantially reflecting wavelengths longer than about 950 nm, and substantially transparent to wavelengths, wavelengths below 950 nm, and the surface opposite to the surface of one input a reflective coating for wavelengths longer than 400 nm, the photovoltaic cell being included in the transparent matrix.
- US Pat. No. 4,088,508 describes an energy amplifier device adaptable to a solar cell, comprising a matrix inside which fluorescent substances are dispersed.
- US Pat. No. 4,110,0123 describes a photovoltaic converter, in which light is collected in a light concentrator comprising a transparent layer, the refractive index is greater than that of the ambient medium and which contains the fluorescent centers and is made to a solar cell, characterized in that more than one solar cell concentrator / combination is stacked on top of each other through a medium having a lower refractive coefficient than that of the concentrator, each concentrator being adapted to convert part of the incident spectrum into fluorescent light and supply it to a solar cell.
- US Pat. No. 754,157 discloses a photovoltaic cell having improved conversion properties.
- the cell includes a cover for a photovoltaic device.
- the cover includes a fluorescent material that shifts the wavelength of a portion of the incident light to be closer to the wavelength that produces the least thermal load on the photovoltaic device.
- the cover comprises a fluorescent material between two reflecting filters. The cell and the lid can be placed together in a stack or separated together
- the invention relates, according to its most general meaning, to an optically active coating for improving the photosolar conversion efficiency, in accordance with the main claim.
- It is for example constituted by a transparent matrix containing a plurality of optically active constituents absorbing light energy in a first lambda A1 absorption wavelength and retransmitting the energy in a second lambda wavelength R1 different from lambda A1 , said optically active constituents being chosen so that the lambda retransmission wavelength R1 of at least one type of constituent corresponds to the length of lambda.
- the invention relates in particular to an optically active coating for improving the photosolar efficiency for the optimization of the efficiency of a photovoltaic cell, characterized in that it comprises N types of constituents C0A stored where the wavelength retransmission rate is less than the absorption wavelength, where N is equal to 3 or 5, the concentration C n of the rank N constituents being between 0.4N and 0.6N, the matrix containing in addition a component C0A anti8tockes where the wavelength of retransmission is smaller than the wavelength of absorbtion.
- the type of optically active constituents of the highest rank N has a retransmission wavelength whose peak is located between 945 nanometers and 980 nanometers.
- said matrix consists of a film of ethylene-vinyl acetate or poly methyl methacrylate.
- said matrix consists of a methyl methacrylate or silicone resin.
- said matrix is constituted by a polyvinyl chloride film.
- said matrix consists of a film consisting of a copolymer comprising 80% and 90% low density polyethylene and 10% to 20% ethylene vinyl acetate.
- said matrix consists of polyvinylidene fluoride.
- the invention also relates to a photovoltaic module characterized in that it comprises at least one photovoltaic element associated with an optically active coating in accordance with one of the abovementioned coatings.
- this module further comprises COA antlstockea components where the retransmission wavelength is between 550 and 800 nanometers is less than the absorption wavelength is between 1000 and 1500 nanometers.
- the module comprises a reflective rear face, the photovoltaic element being encapsulated in an optically doped matrix to form said coating.
- the module according to the invention comprises a plurality of photovoltaic elements forming a matrix with an expansion between 0.25 and 0.75, the areas between said photovoltaic elements being transparent.
- the matrix encapsulating the photovoltaic elements include remanent compounds making it possible to restore light in the absence of insolation.
- the invention also relates to optically active granules for the production of coating, in particular films according to the invention, characterized in that they consist of a transparent matrix containing a plurality of optically active constituents absorbing 1 light energy. in a first absorption wavelength lambdaAl and re - emitting the energy in a second wavelength lambdaR1 greater than lambdaAl, said optically active components being selected so that the retransmission wavelength lambdaR1 from minus one Type 3. Consistency of the absorption wavelength of at least one second type of
- concentration C1 of the optically active components of a first type with respect to the concentration C2 of the optically active constituents of said second type is between 0.1 and 0.2;
- Ci denoting the concentration in moles per liter of component i with respect to the matrix of
- the granules are advantageously produced from high-grade EVA type polymers or polyvinyl chloride (PVC) doped or polyvinylidene fluoride.
- FIG. 1 represents a sectional view of a doped matrix according to the invention
- FIG. 2 represents a schematic view of the incident and outgoing spectrum of a doped material according to the invention
- FIG. 1 represents a sectional view of a doped interface according to the invention. It consists of a transparent matrix containing constituents opc [u. sTie ac fs x * e xen es ⁇ s *
- the interface is applied to the surface of a photovoltaic cell (2) of known type
- the matrix is constituted by a rigid or flexible organic material, or in the form of an applicable coating in the form of a resin.
- the organic material is chosen in particular from; poly (methyl methacrylate) (PMMA)
- EVA polyethylene vinyl acetate
- PC polycarbonate
- LDPE Low density polyethylene
- PVDF Polyvinylidene fluoride
- optically active dopants are chosen from: organic phosphors, (Stokes effect)
- perylene or derivatives pentacene, or diphenyl type organic phosphors, carbazol stylbene or derivatives, chosen in such a way that the emission spectra of one correspond to the absorption spectra of the others.
- the perylene is a chemical compound having the formula C 20 H 2 or C 32 H 1S eg. It is a polycyclic aromatic hydrocarbon presenting as a brown solid.
- Perylene emits a blue or red fluorescence, which makes it a blue or red dopant for organic light emitting diodes, whether substituted or not. It is also an organic photoconductor. It exhibits an absorption maximum at 434 nm with a molar extinction coefficient of 38,500 M-lcm-1 at 435,75 nm, and is poorly soluble in Water (1.2 * 10-5 mmol / l), like all other polycyclic aromatic compounds.
- Pentacene is a chemical compound of formula C22H14 belonging to the family of polycyclic aromatic hydrocarbons (PAHs) and formed from five benzene rings fused linearly. Its extensive conjugated structure and crystalline structure make it a good organic p-type semiconductor (electron donor). Excitons are formed by absorption of ultraviolet or visible radiation, which makes it very sensitive to oxidation: this is the reason why, when it has the appearance of a red powder when it is has just been synthesized, it turns little by little to green in the open air and in the light.
- PAHs polycyclic aromatic hydrocarbons
- Pentacene is a promising material in the production of "thin-film transistors" type transistors and organic field effect transistors.
- the motility of the holes is 5.5 cm 2 ⁇ -l ⁇ s-1, almost at the level of the amorphous silicon. It forms p-n junctions with fullerene C60 used to produce organic photovoltaic cells
- N component 5,12-bis (phenylethynyl) naphthacene, also abbreviated as BPEN, is a polycyclic aromatic hydrocarbon of formula C34H20 used as a fluorochrome for chemiluminescent tubes; it emits an orange light. It is an organic n-type semiconductor.
- the purpose of the system according to the invention is to mobilize at a silicon photocell, for example, mainly sensitive to light radiation between 700 and 950 nm, an incident energy higher than that normally provided by sunlight in this wavelength band.
- the solar energy used is defined by the area of overlap of the emission spectra of sunlight and absorption of the solar cell.
- the process used transforms high-frequency photons (250 to 700 nm) into low-frequency photons (700 - 950 nm) by using the fluorescent properties of certain chemical compounds that are used as intermediates in the transport of energy from light. solar.
- the substances are chosen so that their absorption spectra constitute successive zones, making it possible to cover the entire solar spectrum in the zone (250-700 nm) (frequency or wavelength overlap).
- a luminous radiation of determined wavelength ⁇ p could be absorbed by the substance whose absorption spectrum comprises this value of ⁇ .
- the hvn or hc / In photons that allowed to excite the molecules of this substance are thus definitively extracted from the incident beam. But the unstable state that has been conferred on the molecules is of very short duration.
- the return to the ground state can be carried out in part (statistical expression of the phenomenon and advantageously in our case, by a radiative emission (fluorescence / phosphorescence).
- a radiative emission fluorescence / phosphorescence
- thus generated correspond to the absorption spectrum of another substance that will take over.
- a given substance will be able to absorb either the emission of the substance which precedes it in the sequence of products used (transformed energy), or the part of the emission of the corresponding solar spectrum (non-transformed energy).
- the chemical compounds are trapped in a suitable matrix.
- the matrix will have to be applied on the battery so as to constitute a photon transformer, intermediate between the battery and the light source.
- the different types of chemical compounds are dispersed in the matrix homogeneously.
- the emission of chemical intermediates occurring in all directions, the emission of A (for example) is captured by molecules B located either between A and the cell, or between A and the source, ( and so on) .
- the low frequency photons finally produced per unit of time go half toward the stack and half in the opposite direction (the photons emitted in a plane parallel to the stack being negligible).
- the chemical substances used will have high quantum fluorescence (or phosphorescence) yields and must not give rise to photochemical processes that are susceptible for altering the nature (and hence efficiency) of the photon transformer.
- the table below represents various examples of formulas and their composition and the concentration of the optically active constituents in a PMMA plate with a thickness of three millimeters (in gr / kg and in mole / liter) :
- Table below shows various examples of formulas and composition and concentration of optically active constituents in a film f encapsulation EVA having a thickness of e 900 ⁇ (in gr / kg mol / liter);
- the optically active granules of 1 to 2 mm in diameter consist of optically active molecules (MOAs) integrated directly into different polymers of PMMA, EVA, PVC, PE types. They make it possible to realize coatings, films of displacement of luminous cascade (CL) for the various agricultural and photovoltaic applications.
- MOAs optically active molecules
- the MOAs are included in a medium compatible with them, such as PMMA, in which the optoelectronic characteristics of the MOAs / CLs are perennial.
- the doped PMMA CL is micronized or pulverulent by a cryomilling technique and brought to the dimensions of a few tens of microns to use it as a stable organic pigment containing all or part of the useful MOAs.
- This PMMA matrix is mixed in the EVA granules at the time of extrusion of the film.
- the 2013E formula is then given as an example.
- the concentration level of powdered PMMA is 10%.
- the particle size of the doped PMMA powder is 2 microns and the dopant concentration is 5 grams / kg of CL PMMA premix.
- the matrix located beneath the cells on the face opposite to that of the photon collection may advantageously be constituted by ethyl vinyl acetate, for example encapsulating the photovoltaic cells (cells) and rendered reflective by inclusion.
- the matrix located below the cells and encapsulating the photovoltaic elements can be made reflective and remanent both according to an exemplary embodiment, by the inclusion (doping) of residual compounds such as Cu-doped ZnS inorganic crystals for example to restore the light in darkness for a long time> one hour, for example after the interruption of the incident electromagnetic energy (light excitation)
- the matrix beneath the cells encapsulating the photovoltaic elements can also be made anti-Stokes by the inclusion of Reidel-de Ha ⁇ n Green UC2 rare earth oxysulfide particles or RP YF3YbEr.
- the back substrate (or backsheet) of the photovoltaic module may consist of a polyfluorinated polymer such as polyvinylidene fluoride (PVDF) doped as the encapsulation matrix located beneath the cells with Ti02, and / or ZnS: Cu, and / or Green UC2 rare earth oxysulfide to confer the complementary functions of Reflectance and / or Remanence and or anti-Stokes in bands of length d wave complementary to those of the encapsulation matrices of the front side doped Stokes type light cascades.
- PVDF polyvinylidene fluoride
- the diffusing matrices amplified the efficiency and the efficiency of the light cascades.
- the light cascades are associated with diffusing charges, Si0 2 , Si0 3 , zeolite alumino silicate, mesoporous silica.
- EVA films are also interesting because of their intrinsic diffusion coefficient.
- the mesoporous materials have a contact surface of the order of 1000 m 2 / Gr / cm -1 are good candidates for the grafting of optically active molecules (MOA) / light cascades (CL), their light fastness and their phyisco-chemical inertia. .
- the formulas RREFLEC 2010 A ', B' and C 'in Table 3 are of this technique.
- EVA Film below the Cells Optically Active Reflector in gr / kg ep. 450 ⁇ m of EVA and / or doping of the PVDF substrate (Vinylidene PolyFluoride backsheet).
- the outer layer to the sun is doping UV to blue and the inner layer is doping emitting in the band 600 up to 700 nm.
- the outer layer is more particularly dedicated to the first frequency shift, which also acts as a UV protection.
- This technique is new by the coextrusion technique, simultaneous films of different qualities by the same machine. It adapts to coextruded agricultural films composed of a 600-700 nanometer doped central core otherwise treated with thermal or diffusing and the active outer layer in 400 up to 500 nanometer also treated with antioxidant or hydrophobic.
- the choice of films are suitable for searching for conjugated or complementary optoelectronic effects favorable to the growth of the plants and / or to the optical functions of insect polinators.
- the formulas below are adapted to the use of agricultural films for market garden plants, central core and outer layer.
- CL materials consisting of 2 specialized layers for tomatoes and cucumbers market gardening.
- the central core 1 is the film in 80 micron, while the outer layer is 60 micrometer.
- the film used is 4TT.
- the dosing of the films with complete doping for the PPO and the QB of the formulas P0012 and 013 is repeated, but with concentrations brought back to values corresponding to ⁇ films,
- Dilute solution must have good conditions to have absorptions undisturbed by molecular associations.
- the other concentration rule to be highlighted is that of the relative number of MOA1 / MOA2 / MOA3 / MOA4 / MOA n-1 with respect to each other. This concentration varies from one molecule to another depending on its molecular weight.
- PAH type benzenic their concentrations vary in 10-3, 10-4, 10-5 ....
- aromatic nuclei Anthracene 3phi (10-3) + Naphthalene 4phi (10-4) + pentacene 5phi (10-5) ...
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Abstract
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FR1256849A FR2993409B1 (fr) | 2012-07-16 | 2012-07-16 | Revetement optiquement actif pour l'amelioration du rendement de conversion photosolaire |
PCT/FR2013/051707 WO2014013186A1 (fr) | 2012-07-16 | 2013-07-16 | Revetement optiquement actif pour l'amelioration du rendement de conversion photosolaire |
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US (1) | US9520521B2 (fr) |
EP (1) | EP2873099A1 (fr) |
FR (1) | FR2993409B1 (fr) |
WO (1) | WO2014013186A1 (fr) |
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FR3069863B1 (fr) * | 2017-08-02 | 2020-07-31 | Univ Maine | Materiau pour le dopage optique de substrat polymere |
EP3882017A1 (fr) | 2020-03-20 | 2021-09-22 | Daios, Asterios | Film multicouches en plastique pour utilisation agricole |
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FR2346858A1 (fr) * | 1976-03-31 | 1977-10-28 | Gravisse Philippe | Dispositif amplificateur d'energie rayonnante |
US5078462A (en) * | 1986-11-25 | 1992-01-07 | Gravisse Philippe E | Process and screen for disturbing the transmission of electromagnetic radiation particularly infra-red radiation |
FR2607936B1 (fr) * | 1986-12-04 | 1989-03-03 | Philippe Gravisse | Procede de contre-mesure dans le domaine de la designation d'objectifs et de la telemetrie laser, materiaux et dispositifs pour la mise en oeuvre dudit procede de contre-mesure |
US5646397A (en) * | 1991-10-08 | 1997-07-08 | Unisearch Limited | Optical design for photo-cell |
FR2792461B3 (fr) * | 1999-04-19 | 2001-06-29 | Biocube | Generateurs photovoltaiques a cascade lumineuse et variation de flux elecromomagnetique |
US20100186801A1 (en) * | 2007-03-13 | 2010-07-29 | Basf Se | Photovoltaic modules with improved quantum efficiency |
WO2009157879A1 (fr) * | 2008-06-26 | 2009-12-30 | National University Of Singapore | Dispositif photovoltaïque |
US20100139749A1 (en) * | 2009-01-22 | 2010-06-10 | Covalent Solar, Inc. | Solar concentrators and materials for use therein |
FR2956775B1 (fr) * | 2010-02-19 | 2012-03-09 | Physique Du Rayonnement Et De La Lumiere Lprl Lab De | Modules photovoltaiques pour serre agricole et procede de fabrication de tels modules |
US20110253198A1 (en) * | 2010-03-04 | 2011-10-20 | Western Washington University | Luminescent solar concentrator |
CA2829242A1 (fr) * | 2010-08-07 | 2012-02-16 | Arjun Daniel Srinivas | Composants de dispositifs comprenant des additifs incorpores en surface et procedes de fabrication correspondants |
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2012
- 2012-07-16 FR FR1256849A patent/FR2993409B1/fr active Active
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2013
- 2013-07-16 US US14/415,053 patent/US9520521B2/en not_active Expired - Fee Related
- 2013-07-16 WO PCT/FR2013/051707 patent/WO2014013186A1/fr active Application Filing
- 2013-07-16 EP EP13744756.1A patent/EP2873099A1/fr not_active Withdrawn
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US20150270427A1 (en) | 2015-09-24 |
US9520521B2 (en) | 2016-12-13 |
FR2993409B1 (fr) | 2015-04-10 |
FR2993409A1 (fr) | 2014-01-17 |
WO2014013186A1 (fr) | 2014-01-23 |
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