Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
• • 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
  • B32B17/10036—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 two outer glass sheets
• • 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
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL 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
  • G02F1/00—Devices 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
  • G02F1/01—Devices 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 
  • G02F1/15—Devices 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
  • G02F1/1514—Devices 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 characterised by the electrochromic material, e.g. by the electrodeposited material
  • G02F1/1523—Devices 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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
  • G02F1/1525—Devices 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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • 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
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to the field of electrochemical devices comprising at least one electrochemically active layer capable of reversibly and simultaneously inserting ions and electrons, in particular electrochromic devices.
• electrochemical devices are used in particular to manufacture glazing whose light transmission and / or energy or light and / or energy reflection can be modulated by means of an electric current.
• energy storage elements such as batteries or gas sensors.
• the electrochromic systems in known manner, comprise at least one layer of a material capable of reversibly and simultaneously inserting cations and electrons and whose states oxidation corresponding to the inserted and uninserted states are of distinct coloration, one of the states being generally transparent.
• TC1 and TC2 are electronic conductive materials
• EC1 and EC2 are electrochromic materials capable of reversibly and simultaneously inserting cations and electrons
• EL is an electrolyte material which is both an electronic insulator and an ionic conductor.
• the electronic conductors are connected to an external power supply and the application of a suitable potential difference between the two electronic conductors controls the color change of the system. Under the effect of the potential difference, the ions are disinserted from an electrochromic material and insert into the other electrochromic material through the electrolyte material.
• the electrons are extracted from an electrochromic material to go into the other electrochromic material via the electronic conductors and the external supply circuit to counterbalance the charges and ensure the electroneutrality of the materials.
• the electrochromic system is generally deposited on a transparent medium or not, of organic or mineral nature, which then takes the name of substrate. In some cases two substrates may be used, either each has a part of the electrochromic system and the complete system is obtained by assembling the two substrates, ie one substrate has the entire electrochromic system and the other is intended for protect the system.
• the electroconductive materials are generally transparent oxides whose electron conduction has been amplified by doping such as In 2 O 3 ISn, In 2 O 3 : Sb, ZnO: Al or SnO 2 : F.
• Tin-doped indium oxide In 2 O 3 : Sn or ITO
• one of the electroconductive materials may be metallic in nature.
• tungsten oxide which changes from a blue color to a transparent color according to its insertion state. It is an electrochromic material with cathodic coloration, that is to say that its colored state corresponds to the inserted (or reduced) state and its discolored state corresponds to the uninserted (or oxidized) state.
• an electrochromic material with anodic coloration such as nickel oxide or iridium oxide, the staining mechanism of which is complementary. It follows an exaltation of the luminous contrast of the system. It has also been proposed to use an optically neutral material in the oxidation states concerned, such as, for example, cerium oxide.
• All the aforementioned materials are of inorganic nature but it is also possible to combine organic materials such as electronically conductive polymers (polyaniline ...) or Prussian blue with inorganic electrochromic materials, or even to use only materials organic electrochromes.
• the cations are generally monovalent ions of small size such as H + , Li + but it is also possible to use Ag + or K + ions.
• Electrolytes are generally expected to have high ionic conductivity and to behave passively as the ions pass. Their nature is adapted to the type of ions used for electrochromic switching.
• the electrolytes may be in the form of a polymer or a gel, for example a proton conduction polymer or a lithium ion conductive polymer.
• the electrolyte may also be a mineral layer, in particular based on tantalum oxide. The choice of materials is guided not only by their optical properties but also by considerations of cost, availability, ease of implementation and durability. system. The terms 'durable' and 'durability' are used here in the sense of conserving the luminous properties of systems throughout their use.
• the added material may not fulfill all the conditions normally expected of an electrolyte (for example, possess a lower electrical resistance or be an electrochromic material), the presence of the initial electrolyte guaranteeing the multi-layer or the multi-material as well as created to promote the passage of ions while prohibiting the passage of electrons.
• an electrolyte for example, possess a lower electrical resistance or be an electrochromic material
• Such an example is available in EP-O 867752 A1 concerning an all-solid electrochromic system in which a layer of tungsten oxide has been inserted between the iridium oxide (the electrochromic material) and the oxide of tantalum (the electrolyte).
• the same approach can be employed in the case of the mixed system described in the article by K. S. Ahn et al., Appl. Phys. Lett. 81 (2002), 3930.
• the electrochromic materials are nickel hydroxide and tungsten oxide and the electrolyte is a solid polymer with proton conduction.
• An additional layer of tantalum oxide was inserted between each electrochromic material and the electrolyte polymer because the direct contact caused degradation of the electrochromic materials.
• the multi-layer or multi-material thus created takes the name of electrolyte because it does not participate in the mechanism of insertion and ionic deinsertion.
• the description of such systems can be found, for example, in European patents EP-0 338 876, EP-0 408 427, EP-O 575 207 and EP-0 628 849.
• EP-0 338 876 European patents
• EP-0 408 427 EP-O 575 207
• EP-0 628 849 European patents
• these systems can be arranged in two categories according to type of electrolyte they use:
• the electrolyte is in the form of a polymer or a gel, for example a proton-conductive polymer such as those described in US Pat. EP-0 253 713 and EP-0 670 346, or a conductive polymer of lithium ions such as those described in patents EP-0 382 623, EP-0 518 754 or EP-0 532 408;
• the electrolyte is a mineral layer, in particular based on tantalum oxide and / or tungsten oxide, an ionic conductor but an electronic insulator, which is then referred to as "all solid" electrochromic systems.
• the present invention is more specifically concerned with improvements to electrochemical systems belonging to the all-solid systems category, but it is also intended for mixed systems, or even systems in which all the components are of organic nature.
• Document US Pat. No. 5,552,242 discloses an electrochemical system of the all-solid battery type, the electrolyte of which consists of a hydrogenated silicon nitride.
• the present invention therefore aims to overcome this drawback by proposing an electrolyte for electrochemical system which improves the switching speed.
• the subject of the present invention is an electrochemical system comprising at least one substrate, at least one electroconductive layer, at least one electrochemically active layer capable of reversibly inserting ions, in particular H + , Li type cations. + , Na + , K + , Ag + or OH " anions and at least one electrolyte-functional layer, characterized in that the electrolyte is transparent in the visible and comprises at least one layer of essentially mineral material, in non-transparent form. oxidized, and whose ionic conduction is generated or amplified by incorporation of compound (s) nitrogen (s), in particular nitrided (s), optionally hydrogenated (s) or fluorinated (s). Thanks to the use of such an electrolyte, the electrochemical system has a transition speed (switching between a colored / discolored state and vice versa) singularly improved compared to the electrochemical systems known from the prior art.
• electrolyte according to the invention is easily and rapidly deposited on a substrate by conventional spraying techniques.
• electrolyte in a non-oxidized form offers the advantage of singularly improving the durability of the electrochemical system.
• electrolyte which has been mentioned above, is a material or a set of materials that will transfer ions inserted reversibly by the electrochemically active layer (s) of the system.
• the electrolyte-functional layer is electrically insulating, the electrolyte-functional layer has a visible absorption, for a film of 100 nm, which is less than 20%, preferably less than 10%, and still more preferably less than 5%, the electrolyte-functional layer has a thickness between 1 to 500 nm, preferably between 50 and 300 nm, and even more preferably between 100 and 200 nm,
• the electrolyte-functional layer is based on silicon nitride, boron nitride, aluminum nitride, zirconium nitride, alone or as a mixture, and optionally doped, the electrolyte-functional layer is a multilayer stack, comprising in addition to the nitrogen-containing compound layer (s), at least one further layer of essentially mineral material,
• one of the other layers is chosen from molybdenum oxide (WO 3 ), tantalum oxide (Ta 2 Os), antimony oxide (Sb 2 Os) and nickel oxide (NiO). x ), tin oxide (SnO 2 ), zirconium oxide (ZrO 2 ), aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), niobium oxide (Nb 2 Os), chromium oxide (Cr 2 O 3 ), cobalt oxide (Co 3 O 4 ), titanium oxide (TiO 2 ), zinc oxide (ZnO) ) optionally alloyed with aluminum, tin oxide and zinc oxide (SnZnO x ), the oxide vanadium (V 2 Os), at least one of these oxides being optionally hydrogenated, or nitrided,
• the electrolyte-functional layer is a multilayer stack comprising, in addition to the layer containing nitrogen compound (s), at least one other layer of polymer material,
• the electrolyte-functional layer is a multilayer stack, comprising, in addition to the layer containing nitrogen compound (s) at least one other layer based on molten salts, one of the other layers is chosen from polymers having properties ionic conduction in particular H + , Li + , Ag + , K + , Na + .
• the other layer of the polymer type is chosen from the family of polyoxyalkylenes, especially polyoxyethylene or from the family of polyethylenimines,
• the other layer of the polymer type is in the form of an anhydrous or aqueous liquid or based on gel (s), or of polymer (s), in particular an electrolyte of the hydrogenated compound layer type (s) and / or nitrogen of the type POEiH 3 PO 4 or a layer with hydrogenated compound (s) and / or nitrogen (s) / PEI: H 3 PO 4 , or even more a laminatable polymer.
• the electrochemically active layer comprises at least one of the following compounds: tungsten oxide W, niobium Nb, tin Sn, bismuth Bi, vanadium V, nickel Ni, iride Ir, antimony Sb, tantalum Ta, alone or in admixture, and optionally comprising an additional metal such as titanium, tantalum or rhenium.
• the electrochemical device incorporating in its electrolyte at least one layer according to the invention may be designed so that the electrolyte is actually a multilayer stack.
• the multilayer stack incorporating at least the nitrided layer comprises other polymer-type layers in the form of a polymer or a gel, for example a proton-conducting polymer such as those described in the patent.
• EP-O 253 713 and EP-0 670 346, or a conductive polymer of lithium ions such as those described in patents EP-0 382 623, EP-0 518 754 or EP-O 532 408. It may be also act as an interpenetrating network polymer as described in FR-A-2 840 078.
• the electrolyte can thus be multilayer, and contain layers of solid material or in the form of polymer.
• the single or multilayer electrolyte of the invention has a thickness of at most 5 ⁇ m and in particular of the order of 1 nm to 1 ⁇ m, especially for applications in electrochromic glazings.
• solid material is understood to mean any material having the mechanical strength of a solid, in particular any essentially inorganic or organic material or any hybrid material, that is to say partially mineral and partially organic, as materials that can be obtained by sol-gel deposition from organo-mineral precursors. We then have a system configuration called "all solid” which has a clear advantage in terms of ease of manufacture.
• the system contains an electrolyte in the form of a polymer that does not have the mechanical strength of a solid, for example, it forces to manufacture in fact, in parallel, two "half-cells" each consisting of a carrier substrate coated with a first electroconductive layer and a second electrochemically active layer, these two half-cells are then assembled by inserting the electrolyte between them.
• two half-cells each consisting of a carrier substrate coated with a first electroconductive layer and a second electrochemically active layer
• the manufacturing is simplified, since one can deposit all the layers of the system, one after the other, on a single carrier substrate.
• the device is lightened, since it is no longer necessary to have two carrier substrates.
• the invention also relates to all the applications of the electrochemical device which has been described and which are in particular three in number:
• the first application concerns electrochromic glazings.
• the substrate (s) of the device is (are) transparent (s), glass or plastic, when the glazing is intended to operate in variable light transmission.
• the glazing is intended to operate in variable light transmission.
• the opaque and reflective substrates for example a metal plate
• the device is associated with an opaque element and reflecting
• either one of the electroconductive layers of the device of a metallic nature is selected and sufficiently thick to be reflective.
• the second application relates to energy storage elements, especially batteries incorporating hydrides, which can be used for example in all devices using electronic and / or computer, and all devices requiring a energy storage device of their own, autonomous or not or as a material for the realization of blackout glazing, when the nitride electrolyte is associated with materials whose switching is accompanied by the formation or decomposition of Ti, V, Cr, Mn, Fe, Gd, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd hydride,
• the third application concerns gas sensors.
• This gas sensor can be used, especially in industrial or commercial or domestic environments, as a means of control of physical, chemical, physicochemical measuring instruments. If we return to the first application, that electrochromic glazing, they can advantageously be used as glazing for the building, for automotive, industrial vehicle glazing / public transport, glazing overland transport, air, fluvial or maritime, mirrors, mirrors or as optical elements such as camera lenses, or as a front face or element to be placed on or near the front face of viewing screens. devices such as computers or televisions.
• glass substrates they can be clear or dark glass, flat or curved, reinforced by a chemical or thermal tempering or simply cured. Their thickness can vary between 1 mm and 19 mm, depending on the expectations and needs of end users.
• the substrates may be partially coated with an opaque material, in particular on their periphery, in particular for aesthetic reasons.
• the substrates can also have their own functionality (resulting from a stack of at least one layer of solar control type, anti-reflective, low-emissive, hydrophobic, hydrophilic ...) and in this case the electrochromic glazing combines the functions made by each element to meet the needs of users.
• the polymer interlayer is here used for the purpose of combining the two substrates according to the lamination procedure commonly used in the automotive or building world in order to achieve a safety or comfort product: anti-ejection or anti-seismic safety. balls for use in the field of transport and burglar-proof security (anti-glass breakage) for use in the field of buildings, or providing through this lamination interlayer, acoustic functionality, anti-solar, or staining.
• the lamination operation is also favorable in the sense that it isolates the functional stack against chemical or mechanical aggression.
• the interlayer is preferably selected based on ethylene vinyl acetate (EVA) or its copolymers, it can also be polyurethane (PU), polyvinyl butyral (PVB) thermally crosslinkable resin or one-component thermally (epoxy, PU) or ultraviolet (epoxy, acrylic resin).
• EVA ethylene vinyl acetate
• PVB polyvinyl butyral
• the lamination interlayer is generally transparent, but it can be colored totally or partially to meet the wishes of the users.
• the insulation of the stack from the outside is generally completed by seal systems placed on the fields of the substrates, or even partially inside the substrates.
• the lamination interlayer may also include additional functions such as including an anti-solar function provided for example by a plastic film comprising ITO / Metal / ITO multilayers or a film composed of a stack of organic layers.
• the devices of the invention used as a battery can also be used in the field of building or vehicles, or be part of devices like computers, televisions, or phones.
• the invention also relates to the method of manufacturing the device according to the invention: the electrolyte layer of the invention forming part of the electrolyte can be deposited by a technique using vacuum, of the cathode sputtering type, possibly assisted by a magnetic field, by thermal evaporation or assisted by an electron flow, by laser ablation, by CVD (Chemical Vapor Deposition), possibly assisted by plasma or by microwaves.
• the electrolyte layer of the invention forming part of the electrolyte can be deposited by a technique at atmospheric pressure, in particular by deposition of layers by sol-gel synthesis, in particular of the quenched type, spray-coating or laminar coating or by CVD (Chemical Vapor Deposition) plasma at atmospheric pressure ; It may also be a pyrolysis technique in the liquid or powder phase, or gas phase pyrolysis CVD type but at atmospheric pressure.
• the electrolyte layer can be deposited by reactive sputtering in an atmosphere containing the nitrogenous compounds or their "precursors".
• precursors are understood to mean molecules, compounds which are capable of interacting and / or decomposing under certain conditions in order to form the desired nitrogenous compound in the layer.
• a gaseous precursor may be introduced into the spray chamber, in particular based on NH 3 or more generally on a nitrogen-based precursor, especially in the form of an amine, imine, hydrazine, N 2 .
• the electrolyte layer according to the invention can also be deposited by thermal evaporation, as mentioned previously. It can be assisted by an electron beam, the hydrogenated compounds and / or nitrogen or their "precursors" being introduced into the layer in gaseous form and / or being contained in the material to be evaporated.
• the electrolyte layer according to the invention can also be deposited by a sol-gel type technique.
• the control of the content of hydrogenated and / or nitrogenous compounds is obtained by various means: the composition of the solution can be adapted to contain these compounds or their "precursors", to that of the atmosphere where the deposit. This control can also be refined by adjusting the deposition / hardening temperature of the layer.
• FIG. 1 is a front view of face 2 which is the subject of the invention
• FIG. 2 is a sectional view along AA of FIG. 1,
• FIG. 3 is a sectional view along BB of FIG. 1
• FIG. 4 presents a graph illustrating the switching speed of an electrochemical system according to the prior art compared to that of an electrochemical system incorporating an electrolyte according to FIG. 'invention
• FIG. 5 presents a graph illustrating the influence on the switching speed of an electrolyte according to the invention.
• FIGS. 1, 2 and 3 relate to electrochromic glazing 1. It comprises successively, from the outside to the inside of the cabin, two glasses S1, S2, which are clear glasses (they can also be tinted) silico-sodo-calcium of 2.1 mm respectively; 2.1 mm thick for example.
• the glasses S1 and S2 are of the same size and their dimensions are 150 mm x 150 mm.
• the glass S1 shown in FIGS. 2 and 3 comprises, on the face 2, a stack of electrochromic-type thin layers that are all solid.
• the glass S1 is laminated to the glass S2 by a thermoplastic sheet of polyurethane (PU) 0.8 mm thick (it can be replaced by a sheet of ethylenevinylacetate (EVA) or polyvinylbutyral (PVB).
• PU polyurethane
• EVA ethylenevinylacetate
• PVB polyvinylbutyral
• the "all solid" electrochromic thin film stack comprises an active stack 3 placed between two electronically conductive materials also called current collectors 2 and 4.
• the collector 2 is intended to be in contact with the face 2.
• the collectors 2 and 4 and the active stack 3 may be of substantially identical dimensions and shapes, or of substantially different dimensions and shapes, and it will be understood that the routing of the collectors 2 and 4 will be adapted according to the configuration.
• the dimensions of the substrates, in particular Sl can be substantially greater than those of 2, 4 and 3.
• the collectors 2 and 4 are of the metallic type or of the TCO (Transparent) type.
• Conductive Oxide in ITO, SnO 2 : F, ZnO: A1 or be a multi-layer of the TCO / metal / TCO type, this metal being chosen in particular from silver, gold, platinum, copper. It may also be a multi-layer type NiCr / metal / NiCr, the metal being also chosen in particular from silver, gold, platinum, copper. According to the configurations, they can be suppressed and in this case current leads are directly in contact with the active stack 3.
• the glazing 1 incorporates current leads 8, 9 which control the active system via a power supply. These current leads are of the type used for heated glazing (ie foil, wire or similar).
• a preferred embodiment of the collector 2 is to deposit on the face 2 a first 50 nm SiOC layer surmounted by a second SnO 2 : F layer of 400 nm (two layers preferably deposited successively by CVD on the float glass before cutting).
• a second embodiment of the collector 2 consists in depositing on the face 2 a bilayer consisting of a first layer doped with SiO 2 doped or not (in particular doped with aluminum or boron) of about 20 nm surmounted by a second layer of ITO of about 100 to 600 nm (two layers preferably deposited successively, under vacuum, by magnetic field assisted sputtering and reactive in the presence of oxygen, possibly in the hot state).
• collector 2 consists in depositing on the face 2 a monolayer consisting of ITO of approximately 100 to 600 nm (a layer preferably deposited, under vacuum, by magnetic field assisted sputtering and reactive in the presence of oxygen possibly hot)
• the collector 4 is a 100 to 500 nm ITO layer also deposited by magnetic field assisted reactive sputtering on the active stack.
• the active stack 3 shown in FIGS. 2 and 3 is broken down as follows: • a layer of nickel oxide electrochromic anodic material of
• the layer of anodic material is based on an iridium oxide layer of 40 to 100 nm.
• a layer of cathodic electrochromic material based on hydrated tungsten oxide of 200 to 500 nm, preferably 300 and 400 nm, in particular close to 370 nm, the active stack 3 may be incised on all or part of its periphery of grooves made by mechanical means or by laser radiation attack, possibly pulsed, in order to limit peripheral electrical leakage as described in the French application FR-2 781 084.
• the glazing shown in FIGS. 1, 2 and 3 incorporates (not shown) in the figures) a first peripheral seal in contact with the faces 2 and 3, this first seal being adapted to provide a barrier to external chemical attack.
• a second peripheral seal is in contact with the edge of Sl, the edge of S2 and the face 4, so as to provide: a barrier, a mounting means with the vehicle, a seal between the inside and the outside, a aesthetic function, a means of incorporating reinforcement elements.
• FIG. 4 see curve 1
• the variation of light transmission measured at the center of the glazing is shown when the glazing is subjected to a coloration / fading cycle using a voltage slot. If this active stack is powered, using a voltage slot, it can be seen that the glazing, with an electrolyte according to the prior art, takes about 80 seconds to go from a colored state to a discolored state. (We can refer to Figure 4).
• one of the oxide-based layers constituting the electrolyte is substituted with a layer according to the methods of the invention, that is to say a layer of a thickness between 10 nm and 300 nm, silicon nitride, boron nitride, aluminum nitride, zirconium nitride, alone or in mixture, and optionally doped, it can be seen while the glazing goes from a state colored to a faded state in less than 15 s, for the same voltage window and all things being equal. It is also noted that the coloring speed is higher (refer to the slope at the origin which is very pronounced in the curve 2).
• FIG. 5 shows the variation of light transmission measured at the center of the glazing as a function of time, this glazing comprising an active stacking structure conforming to that previously described for which the electrolyte layer is either a single layer according to the methods of the invention (curve 1) is a bi-layer based on inorganic oxide and an electrolyte layer according to the methods of the invention (curve 2).
• the layer according to the invention is associated with a layer based on inorganic oxide.
• the electrolyte layer is inserted according to the methods of the invention between two mineral oxide electrolyte layers. It is thus possible for example to have Ta 2 O 5 / the layer according to the invention / Ta 2 O 5
• the active stack 3 "all solid" can be replaced by other families of electrochromic polymer type.
• this polymer is particularly stable, especially with UV, and operates by insertion-deinsertion of lithium ions (Li + ) or alternatively of H + ions.
• a second part acting as an electrolyte and formed of a layer of thickness between 50 nm to 2000 ⁇ m, and preferably between 50 nm to 1000 ⁇ m, is deposited by a known technique of liquid deposition ( spraying or "spray coating”, dip coating or “dip coating”, rotary spraying or “spin coating” or casting, between the first and third parts on the first part or by injection.
• This second part is based on polyoxyalkylene, in particular Alternatively, it may be a mineral type electrolyte, based for example on hydrated oxide of tantalum, zirconium, or silicon.
• a current collector conductive son, conductive son + conductive layer, conductive layer only
• this all-polymer electrochromic stack it is proposed to substitute for one of the layers forming the electrolyte, at least one layer with a similar function but according to the methods of the invention.
• a layer according to the methods of the invention is inserted between one of the active layers and one of the layers forming the electrolyte or in the middle of the layers forming the electrolyte.
• this insertion can take the following configuration: a layer according to the methods of the invention between one of the active layers and one of the layers forming the electrolyte or in the middle of the layers forming the electrolyte.
• This example corresponds to a glazing operating by proton transfer. It consists of a first glass substrate 1, made of 4 mm silico-soda-lime glass, then successively:
• a first layer of NiO x H 5 hydrated nickel oxide electrochromic material of 185 nm (it could be replaced by a layer of iridium oxide hydrate of 55 nm),
• a bi-layer electrolyte polymer-based usually used in this type of glazing which is "doubled" with a layer of hydrated tantalum oxide sufficiently conductive not to penalize the transfer of protons via the polymer and which protects the counter electrode of anodic electrochromic material from direct contact with the latter, the intrinsic acidity of which would be detrimental to it.
• a tri-layer electrolyte with two layers of hydrated oxide, either on either side of the polymer layer, or superimposed on each other on the side of the layer of anode electrochromic material.
• at least one of the electrolyte function layers based on tantalum oxide, antimony, tungsten is replaced by at least one layer of non-oxidized electrolyte according to the invention.
• the layer according to the invention is inserted into a solid solution of POE-H 3 PO 4 or PEI-H 3 PO 4
• the electrolyte is combined with a stack of layers based on hydride materials, capable of switching in light transmission or in light reflection for which the switching is accompanied by the formation or decomposition of hydrides.
• the active stack 3 is broken down as follows: a layer of 20 to 100 nm composed of a transition metal and in particular magnesium to which can be combined another transition metal and in particular nickel, cobalt or nickel.
• manganese a layer according to the invention, that is to say that is to say a layer with a thickness of between 10 nm and 300 nm, silicon nitride, boron nitride, nitride of aluminum, zirconium nitride, alone or in mixture, and possibly doped, - optionally a layer of palladium thickness between 1 nm and 10 nm is interposed between the magnesium-based layer and the layer according to the invention, a hydrated tantalum oxide or hydrated silica oxide or hydrated zirconium oxide layer layer of 100 nm or a mixture thereof, a layer of cathodic electrochromic material based on hydrated tungsten oxide of 370 nm .
• a layer according to the invention is located on either side of a palladium layer.
• the active stack thus formed switches in reflection and in transmission, the modification of the aspect in reflection not being the same depending on whether the observer is looking at the side of the hydride layer or the tungsten oxide layer. .
• the potential difference to which the two electroconductive layers 2 and 4 are subjected by the external power supply system is such that the protons are predominantly in the tungsten oxide layer, the latter is colored and the magnesium-based layer is in a metallic and reflective state.
• the light transmittance of the glazing is less than 1% because of the metallic state of the magnesium-based layer, which reflects most of the light.
• the glazing is reflective and weakly colored, with a light reflection of between 40% and 80%, depending on the thickness of the magnesium-based layer. Seen in reflection on the side of the tungsten oxide layer, the glazing appears colored with a light reflection of between 5% and 20%, the color and the level of light reflection depending on the thicknesses of the layers composing the stack and the potential difference applied.
• the potential difference to which the two electroconductive layers 2 and 4 which are associated with the current collectors by the external power supply system (not shown) are subjected is such that the protons are predominantly in the magnesium-based layer it is in a semi ⁇ conductive and discolored state and the tungsten oxide layer is in a discolored state.
• the light transmission of the glazing is maximum, it is between 20% and 50% depending on the thickness of the magnesium-based layer and the presence of a palladium layer.
• the light reflection measured on the side of the magnesium-based layer is between 10% and 30%, as is the light reflection measured on the side of the tungsten oxide layer.
• the changes in the reflection and transmission properties in the visible wavelength range (380 nm - 780 nm) mentioned in the example above are also valid in the infrared (> 780 nm), to know that the reflection and the energetic transmission of the glazings vary in the same way as the reflection and the luminous transmission.
• Some systems also have the particularity of passing through an absorbing intermediate state in which both the light reflection and the light transmission of the magnesium-based layer pass through a minimum.
• the hydride layer based on magnesium described above can be replaced by a layer of hydride based on rare earth (Gd, La, Y %) optionally alloyed with a transition material such as magnesium.
• a transition material such as magnesium.
• One of the current collectors 2 and 4 mentioned in the example may be omitted, in particular one that is in contact with the hydride layer if its electronic conductivity is sufficient.
• the layer according to the invention is used in fuel cells as a medium for the transport of ions, especially H + , or O 2

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