EP2404214A1 - Elektrisch steuerbare vorrichtung mit einheitlicher färbung/verfärbung über die gesamte oberfläche - Google Patents

Elektrisch steuerbare vorrichtung mit einheitlicher färbung/verfärbung über die gesamte oberfläche

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Publication number
EP2404214A1
EP2404214A1 EP10711862A EP10711862A EP2404214A1 EP 2404214 A1 EP2404214 A1 EP 2404214A1 EP 10711862 A EP10711862 A EP 10711862A EP 10711862 A EP10711862 A EP 10711862A EP 2404214 A1 EP2404214 A1 EP 2404214A1
Authority
EP
European Patent Office
Prior art keywords
layers
controllable device
electrically controllable
layer
substrate
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Withdrawn
Application number
EP10711862A
Other languages
English (en)
French (fr)
Inventor
Fabienne Piroux
Emmanuel Valentin
Samuel Dubrenat
Gilles Bokobza
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP2404214A1 publication Critical patent/EP2404214A1/de
Withdrawn legal-status Critical Current

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153Constructional details
    • G02F1/155Electrodes
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1343Electrodes
    • G02F1/13439Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions

Definitions

  • the present invention relates to an electrically controllable device with variable optical / energy properties, comprising the following stack of layers:
  • V 1 a first glass-function substrate
  • a first electronically conductive layer (TCCi) with an associated current supply an electro-active system (EA) comprising or consisting of:
  • At least one electroactive organic compound (eai + ) capable of being reduced and / or of accepting electrons and cations acting as compensation charges;
  • At least one electroactive organic compound (ea 2 ) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said organic compounds electro ⁇ assets (ea + & ea 2) being electrochromic in order to obtain a color contrast; and
  • TCC 2 electronically conductive layer
  • TCC transparent Conductive Coating
  • TCO transparent Conductive Oxide
  • the electroactive medium (EA) is a medium in solution or gelled. It can also be contained in a self-supported polymer matrix as described in the international application PCT / FR2008 / 051160 filed on
  • the two electro-active materials are electrochromic materials, these may be identical or different. In the case where one of the electro-active materials is electrochromic and the other is not, the latter will act as a counterelectrode not participating in the coloring and discoloration of the system.
  • the compound (eai + ) is electrochromic (being, for example, 1,1'-diethyl-4,4'-bipyridinium diperchlorate) and that the compound (ea 2 ) is electrochromic (being, for example, 5, 10-dihydro-5,10-dimethylphenazine) or non-electrochromic being for example a ferrocene)
  • electrochromic being, for example, 1,1'-diethyl-4,4'-bipyridinium diperchlorate
  • the compound (ea 2 ) is electrochromic (being, for example, 5, 10-dihydro-5,10-dimethylphenazine) or non-electrochromic being for example a ferrocene)
  • each current supply consists of a thin conductive strip applied along a border of the associated electrically conductive layer, the two strips being located along two opposite edges of the electrically controllable device.
  • the transition from faded to faded state can be uniform.
  • the Applicant Company has therefore sought an effective means to eliminate curtain or halo effects during the electrochromic glazing coloring process and to ensure a uniform absorption value over the entire surface of an electrochromic glazing in colored and discolored states, and when staining and fading steps, regardless of the size of this glazing.
  • the subject of the present invention is therefore an electrically controllable device with variable optical / energy properties, comprising the stack of layers as defined at the very beginning of this description. characterized by the fact that each of the TCCi and TCC 2 layers is chosen to present a resistance per unit area R n allowing it to present an equipotential surface in coloration and discoloration, each of the layers TCC1 and TCC2 having a variable resistance R n gradually decreasing from the periphery to the inside of the electrically controllable device by choosing R D at the center of the glazing, in the region or regions farthest from the current leads, so that the ohmic drop on the central surface of the substrates of the glazing, in the or the areas furthest away from the current leads, ie not more than five per cent of the value of the voltage applied across the device.
  • Vp V ap pi iqu e - Ri
  • V ap pi ied is the voltage applied to the conductive layer - i is the current
  • the two layers TCC1 and TCC2 facing each other are identical.
  • the TCC1 and TCC2 layers may have a variable resistance R D gradually decreasing gradually along a gradient.
  • the grid or microgrid may be of a metal such as aluminum.
  • the TCCi or TCC 2 layers may have a variable resistance R n decreasing gradually in zones.
  • Variable R D advantageously has a resistance that ranges from 20 ⁇ / D or more at the periphery to 5 ⁇ / D or less at the center of the layer.
  • a TCCl or TCC2 layer may be in the form of a continuous layer or in the form of a grid or a microgrid or in the form of grids or a microgrid coated with a continuous layer.
  • a TCCi or TCC 2 layer with variable resistance R n may have been obtained: by a plasma treatment, a flame or ablation of material from said layer to progressively degrade the conductivity or degrade it by zones;
  • the first deposit being made on the entire surface of the substrate, then the subsequent deposit being made on a central region thereof with masking of the region periphery, and so on if other zones must be formed, the deposits other than the first being able to be made in particular on circular regions so that the different zones of the layer are concentric zones, the center of which corresponds to that of the substrate;
  • a network of identical or different conductive and / or insulative patterns which have been formed on at least a portion of the conductive layer deposited on the substrate.
  • French patent application FR2875669 describes such networks of conductive and / or insulating patterns.
  • TCC1, TCC2 by a more conductive material than the latter, by producing the conductive layer (TCC1, TCC2) with local extra thicknesses forming the pattern network, sufficient thicknesses to obtain the desired characteristics, or by producing portions of a second, more conductive layer (TCC1, TCC2), this second layer being deposited for example by spraying on the layer previously covered with a mask.
  • the conductive patterns include silver points.
  • TCC 2 are in particular metal-type layers, such as layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) type layers, such as tin doped indium oxide layers
  • TCO / metal / TCO multilayers the TCO and the metal being in particular chosen from those enumerated above; or NiC r / metal / NiC r multilayers, the metal being in particular chosen from those enumerated above.
  • the layers TCC1 & TCC2 may each be connected to a current supply constituted by a conductive strip applied to the associated TCC1 or TCC2 layer, the conductive strip possibly being a metal, an alloy or an electrically conductive composite which is deposited directly on the substrate coated with its conductive layer or on a spacer separating the two spacer substrates using for example a vacuum deposition technique or screen printing with a metal paste, or which is welded to the substrate covered with its conductive layer or on a separating spacer the two substrates or else which is adhered by means of an electrically conductive adhesive, the conductive strip applied to a substrate which may be continuous or have discontinuous regions and connected to each other and which may be applied to all or part of each substrate.
  • the current leads comprise in particular continuous conductive strips applied to the layers TCC1 and TCC2 and disposed all around or substantially all around said conductive layers (TCC1 and TCC2).
  • the substrates with glass function can be chosen from glass and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), poly (ethylene terephthalate) (PET), poly (ethylene naphthoate ) (PEN) and cyclosporin copolymers (COC).
  • PMMA poly (methyl methacrylate)
  • PC polycarbonate
  • PET poly (ethylene terephthalate)
  • PEN poly (ethylene naphthoate )
  • COC cyclosporin copolymers
  • a layer or a stack of layers may be arranged between a glass-function substrate, in particular a plastic substrate, and a TCCl or TCC2 layer, this layer or these layers being chosen independently from among the inorganic, organic or organic-inorganic hybrids, and having been deposited on the substrate before the deposition of the associated TCC1 or TCC2 layer in order notably to improve the adhesion of TCC1 or TCC2 to the substrate or to provide an additional function such as impermeability to gases and to moisture.
  • an intermediate layer there may be mentioned a layer of Si 3 N 4 or SiO 2 which in particular acts as a barrier to moisture and oxygen.
  • the electroactive system (EA) can comprise a self-supporting polymer matrix in which the electroactive organic compound (s) (eai + & ea 2 ) and the ionic charges are inserted, said polymer matrix containing in its entirety in a liquid (L) solubilizing said ionic charges but not solubilizing said self-supporting polymer matrix, the latter being chosen to ensure a percolation path of the ionic charges to allow said oxidation and reduction reactions of said electroactive organic compounds (eai + & ea 2 ), the ionic charges being carried by at least one of said electroactive organic compounds (eai + & ea 2 ) and / or reduced and oxidized species which are respectively associated with them (eai and ea 2 + ) and / or by at least one ionic salt and / or at least one acid solubilized in said liquid (L) and / or by said self-supporting polymer matrix; the liquid (L) being constituted
  • the electro-active system may comprise a solution or a gel containing the electroactive organic compounds (eai + & ea 2 ).
  • the electroactive organic compound (s) (eai + ) may or may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4,4'-bipyridinium diperchlorate, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulphides, as well as all the electro-active polymeric derivatives of the electro-active compounds which have just been mentioned ; and the electroactive organic compound (s) (ea 2 ) is or are chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N ', N' -tetramethylphenylenediamine (TMPD), phenothiazines such as phen
  • the ionic salt or salts may be chosen from lithium perchlorate, the salts trifluoromethanesulfonates or triflates, trifluoromethanesulfonylimide salts and ammonium salts; the acid or acids are chosen from sulfuric acid (H 2 SO 4 ), triflic acid (CF 3 SO 3 H), phosphoric acid (H 3 PO 4 ) and polyphosphoric acid (H n + 2 P n 0 3n + 1); the one or more solvents may be chosen from dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and N-methyl-2-pyrrolidone (1-methyl-2); pyrrolidinone), gamma-butyrolactone, ethylene glycols, alcohols, ketones, nitriles and water, the ionic liquid (s) may be chosen from imidazolium salts, such as 1-ethyl-3- methylimi
  • the polymer constituting at least one layer may be a homo- or copolymer in the form of a non-porous film capable of swelling in said liquid, or in the form of a porous film, said porous film optionally being capable of swelling in the liquid having ionic charges and whose porosity after swelling is chosen to allow percolation of the ionic charges in the thickness of the liquid-impregnated film.
  • the polymeric material constituting at least one layer may also be chosen from: the homo- or copolymers which do not comprise ionic charges, in which case they are borne by at least one aforementioned electroactive organic compound and / or by at least one solubilized ionic or acidic salt and / or by at least one liquid ionic or molten salt;
  • the homo- or copolymers comprising ionic charges in which case additional charges making it possible to increase the rate of percolation may be borne by at least one aforementioned electroactive organic compound and / or by at least one solubilized ionic or acidic salt and / or by at least one ionic liquid or molten salt; and
  • mixtures of at least one homo- or copolymer not carrying ionic charges and at least one homo- or copolymer containing ionic charges, in which case additional charges making it possible to increase the percolation rate may be carried by minus an electroactive organic compound mentioned above and / or by at least one ionic salt or solubilized acid and / or by at least one ionic liquid or molten salt.
  • the polymer matrix may consist of a film based on a homo- or copolymer comprising ionic charges, able to give by itself a film essentially capable of providing the desired percolation rate for the electro-active system or a higher percolation rate than this and a homo or copolymer with or without ionic charges, able to give itself a film that does not necessarily ensure the desired rate of percolation but essentially able to ensure the mechanical strength, the contents of each of these two homo- or copolymers being adjusted so that they are insured at the times the desired percolation rate and the mechanical strength of the resulting self-supporting organic active medium.
  • the polymer or polymers of the polymer matrix not comprising ionic charges can be chosen from copolymers of ethylene, vinyl acetate and possibly at least one other comonomer, such as ethylene-vinyl acetate copolymers.
  • EVA ethylene-vinyl acetate copolymers.
  • PU polyurethane
  • PVB polyvinyl butyral
  • PI polyimides
  • PA polyamides
  • PS polystyrene
  • PVDF polyvinylidene fluoride
  • PEEK polyether ether ketones
  • POE polymer matrix bearing ionic or polyelectrolyte charges
  • the polymer (s) of the polymer matrix bearing ionic or polyelectrolyte charges may be chosen from sulphonated polymers which have been exchanged for the ions H + of the SO 3 H groups by the ions of the desired ionic charges, this ion exchange having occurred before and / or simultaneously with the swelling of the polyelectrolyte in the liquid comprising ionic charges, the sulfonated polymers being especially chosen from sulfonated tetrafluoroethylene copolymers, sulfonated polystyrenes (PSS), sulfonated polystyrene copolymers, poly (2 acid -acrylamido-2-methyl-1-propanesulfonic acid (PAMPS), sulfonated polyetheretherketones (PEEK) and sulfonated polyimides.
  • PSS sulfonated polystyrenes
  • the electrically controllable device of the present invention may also have current leads to the respective layers TCC1 and TCC2 consisting of conductive strips applied to the TCC1 and TCC2 layers.
  • the conductive strip may be a metal, an alloy or an electrically conductive composite deposited directly on the substrates covered with a conductive layer, or spacers using for example a vacuum deposition technique, or screen printing with a metal paste or welded to the substrates covered with a conductive layer or spacers or glued with an electrically conductive adhesive.
  • the conductive strips of each substrate may be continuous or discontinuous and interconnected and may be applied to all or part of each substrate.
  • the current leads consist of continuous conductive strips applied to the layers TCC1 and TCC2 and disposed all around or substantially all around said conductive layers (TCC1 and TCC2).
  • the electrically controllable device of the present invention is in particular configured to form: a roof for a motor vehicle, activatable independently, or a side window or a rear window for a motor vehicle or a rearview mirror; a windshield or a portion of a windshield of a motor vehicle or an airplane or a ship, an automobile roof; an airplane porthole; a display panel of graphical and / or alphanumeric information; indoor or outdoor glazing for the building; a roof window; a display stand, store counter; a protective glazing of an object of the table type; an anti-glare computer screen; glass furniture; a partition wall of two rooms inside a building.
  • FIG. 1 is a schematic view of a face of a glazing according to the first prior art
  • FIGS. 4 and 5 are schematic sectional views of two variants of a glazing according to the aforementioned French patent application No. 08/58289, representing the second prior state of the cited technique;
  • FIG. 6 is a sectional view along VI-VI of Figure 5;
  • FIG. 7 and 8 are schematic views illustrating, in a comparative manner, the development of the coloring symbolized by color rectangles, respectively according to the first prior art of the technique cited above and according to the invention;
  • FIGS. 9 and 10 are schematic views illustrating, in a comparative manner, the development of the coloring symbolized according to the second prior art of the technique cited above and according to the present invention.
  • FIG 11 is a schematic front view of an ITO layer glass implemented according to Examples 2 and 4, showing the three different regions of this layer varying according to the value of R n .
  • the glazing unit shown therein comprises two glass plates V1, V2 arranged face to face, one of which is offset downwards in order to meet the objectives of FIG. mounting in the mirror frame.
  • the internal faces of each of these plates V 1 , V 2 are coated with an electronically conductive layer, respectively TCC 1 , TCC 2 , constituted in particular by a TCO (abbreviation of "transparent conductive oxide").
  • the current leads to the respective layers TCC 1 , TCC 2 are made by foils respectively 1, 2, each constituted by an L-shaped metal strip, one of the branches of which is applied to the edge of the coated glass Vi, V 2 and the other leg of which is applied against the TCC1, TCC2 layer portion, protruding from the "reservoir” portion.
  • the foils 1, 2 are applied respectively along the upper edge and along the lower edge of the mirror.
  • the eli + compound will be chosen from 1,1'-diethyl-4,4'-bipyridinium diperchlorate (electrochromic) and, as compound ea 2 , 5,10-dihydro-5,10 dimethylphenazine (electrochrome) or ferrocene (non-electrochromic or counter-electrode not involved in the coloring process of the system).
  • the active medium in which the species eai + and ea 2 are , is colorless, and, when a voltage is applied, the species eai + are reduced to an eal species, the latter being uniformly distributed in the vicinity of the surface of the electrically conductive layer connected to the sign pole of the electrical supply, that is to say say to the cathode of the glazing, and, similarly, the species ea 2 oxidize in species ea 2 + , the latter being distributed uniformly in the vicinity of the surface of the electronically conductive layer connected to the pole of sign + of the power supply, that is to say the anode of the glazing, the panel then appearing in a uniform color corresponding to the uniform mixture of species eai and ea 2 + .
  • This phenomenon of segregation is due to the preferential reduction of the species eai + in species eai towards the zone of greater electrical intensity of the cathode, and, conversely, to the preferential oxidation of the species ea 2 in species ea 2 + towards the zone of greater electrical intensity of the anode, these two zones of greater electric intensity being those of foils.
  • FIG 6 of the accompanying drawing the upper part schematizes a cross section of the known electrically controllable device and its lower part, a front view of the panel tensioned, illustrates this phenomenon by showing the accumulation zones of eai and ea 2 + when the electrically controllable device is put under tension, and, consequently, the appearance of a color mainly due to the eai species towards the cathode (on the right in the front view), this color gradually degrading a new color mainly due to the species ea 2 + to the anode (left on the front view).
  • the phenomenon of segregation is moreover all the more important that the panel of the electrically controllable device is larger, and currently prevents the commercial use of large electrically controllable devices, such as electrically controllable glazing for the building.
  • a glazing unit according to the French patent application No. 0858289 is shown, this latter comprising two opposing glass sheets, Vi, V 2 , each coated of their layers respectively TTC1 and TTC 2 separated by a spacer frame 3 in double-sided adhesive with a polyester core and closed by an outer encapsulation seal J.
  • the frame 3 and the two coated glass sheets delimit the internal receiving space from the EA medium.
  • a current conducting conductive strip which has a length 1 along a border as in the case of the prior art of FIGS. 1 to 3, but extending by three successive lengths respectively la, Ib and Ic and 2a, 2b and 2c, each in the vicinity of one of the remaining three borders.
  • the aforementioned thin strips are folded on themselves each time by 90 ° at the corners. They are opposite the spacer frame 3, facing each other in the variant of FIG. 4 but slightly offset from one another in the variant of FIG. 5.
  • the assembly of the glazing and the encapsulation of the EA medium is done in a conventional manner, the current supply strips having previously been welded or glued on the periphery of the corresponding coated glass sheet.
  • PVDF polyvinylidene fluoride - ITO: indium oxide doped with tin In 2 O 3 : Sn
  • the "K-glass®” glass used in the examples is a glass coated with an electroconductive layer of SnO 2 IF (glass marketed under this name by the company "Pilkington”).
  • the "VG40" glass used in the examples is a tinted glass having a light transmission, TL, of 54%, of the Venus Thermocontrol® range from Saint Gobain Sekurit.
  • TL light transmission
  • the polyvinylidene fluoride powder manufactured by the company "Arkema” under the name “Kynarflex® 2821” was used.
  • - Discolored TL means the light transmission of the discolored sample after applying zero voltage for 3 minutes, averaged over the spectrum visible, ie between 380 nm and 780 nm, and measured on a Minolta 3700D spectrometer;
  • - colored TL means the light transmission of the colored sample after applying a voltage of 1.5V for 3 minutes, averaged over the visible spectrum, ie between 380nm and 780nm, and measured on a Minolta 3700D spectrometer
  • the fading time is the time required to change from TL colored to TL colored + 90% x (TL discolored - TL colored).
  • the color time is the time required to change from discolored TL to discolored TL - 90% x (discolored TL - colored TL).
  • Electroactive system PVDF + ferrocene + 1,1'-diethyl-4,4'-bipyridinium diperchlorate + lithium triflate + propylene carbonate
  • a self-supporting PVDF film was made by mixing 6.5 g of PVDF powder, 13.0 g of dibutyl phthalate, 0.5 g of nanoporous silica and 25 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a net of water. The film thus obtained has a thickness of about 200 microns.
  • An electroactive solution was prepared by mixing 0.17 g of ferrocene, 0.37 g of 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 0.28 g of lithium triflate in 30 ml of propylene carbonate. The solution was stirred for 1 hour.
  • the PVDF film about 200 microns thick, was immersed for 5 minutes in diethyl ether (to solubilize dibutyl phthalate) and then for 5 minutes in the electroactive solution before being deposited on a glass plate.
  • diethyl ether to solubilize dibutyl phthalate
  • electroactive solution before being deposited on a glass plate.
  • "K-glass ®” A second "K-glass ®” plate was deposited on the electrolyte-impregnated film, a PET frame was used as a spacer around the electro-active medium and clamps were used to ensure a good contact between the glass and the movie.
  • the electrochromic device thus manufactured has an active surface of 22 ⁇ 23 cm 2 and its performance is reported in Table 1 below:
  • ITO layer glass with different R D regions : 20, 10 and 5 ⁇ / D r as shown in Figure 11
  • a variable surface resistance ITO conductive layer was made by performing three ITO sputter deposition on the same substrate.
  • the ITO is deposited on the entire surface of the substrate and the deposited thickness of 180nm allows to have a R n ⁇ 20 ⁇ / D.
  • a PET mask is used to protect the substrate with the exception of a central circle of diameter 15cm.
  • the thickness deposited during this second deposit is 90nm, which makes it possible to reach an R n
  • a PET mask is used to protect the substrate except for a central circle of diameter 6cm.
  • the thickness deposited during this third deposit is 240 nm, which makes it possible to reach a
  • An electroactive solution was prepared by mixing 0.25 g of 5,10-dihydro-5,10-dimethylphenazine, 0.50 g of 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 47 g of lithium triflate in 20 ml of propylene carbonate. The solution was stirred for 1 hour.
  • An electrochromic device having an active surface area of 22 ⁇ 23 cm 2 was manufactured as described in Example 1 and the performance of which is given in Table 3 below:
  • EXAMPLE 4 (according to the invention): Preparation of an electrochromic cell
  • Electroactive system of Example 2 ITO layer glass with R D varying between 20, 10 and 5 ⁇ / D of Example 2

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
EP10711862A 2009-03-02 2010-03-02 Elektrisch steuerbare vorrichtung mit einheitlicher färbung/verfärbung über die gesamte oberfläche Withdrawn EP2404214A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0951309A FR2942665B1 (fr) 2009-03-02 2009-03-02 Dispositif electrocommandable a coloration/decoloration homogene sur toute la surface
PCT/EP2010/052620 WO2010100147A1 (fr) 2009-03-02 2010-03-02 Dispositif electrocommandable a coloration/decoloration homogene sur toute la surface

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EP2404214A1 true EP2404214A1 (de) 2012-01-11

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US (1) US20110317243A1 (de)
EP (1) EP2404214A1 (de)
JP (1) JP2012519308A (de)
KR (1) KR20110126125A (de)
CN (1) CN102341750A (de)
FR (1) FR2942665B1 (de)
WO (1) WO2010100147A1 (de)

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KR20110126125A (ko) 2011-11-22
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US20110317243A1 (en) 2011-12-29
WO2010100147A1 (fr) 2010-09-10
CN102341750A (zh) 2012-02-01
FR2942665B1 (fr) 2011-11-04

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