Classifications

• • 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
  • G02F1/1524—Transition metal compounds
  • G02F1/15245—Transition metal compounds based on iridium oxide or hydroxide
• • 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
  • G02F2202/00—Materials and properties
  • G02F2202/16—Materials and properties conductive

Definitions

• the subject of the present invention is an electro-chemical and / or electrically-controllable device of the glazing type and with variable optical and / or energy properties .
• glazings There is in fact currently an increased demand for so-called “smart" glazings that are capable of adapt to the needs of users.
• “intelligent” B windows this may be the control of the solar input through glazings mounted outdoors in buildings or vehicles of the car, train or airplane type (porthole for example). is to be able to limit an excessive heating inside the cockpits / premises, but only in case of strong sunshine.
• glazing can also be the control of the degree of vision through glazing, especially in order to obscure them, to make them diffuse or even to prevent any vision when it is desirable.
• This may concern glazing mounted in interior partitions in premises, trains, planes or mounted in automotive side windows. This also applies to mirrors used as mirrors, to punctually avoid the driver to be dazzled, or signs, so that messages appear when necessary, or intermittently to better attract attention. Glazing that can be rendered at will scattering can be used when desired as projection screens.
• it may be the generation of light through the glazing to control the level of brightness or color generated.
• it may be the generation of light through the glazing to control the level of brightness or color generated.
• electro-controllable systems for such aspect changes / thermal properties.
• Electrochromic material generally comprise two layers of electrochromic material separated by an electrolyte layer and framed by two electroconductive layers, the latter being associated with current leads connected to a power supply.
• Each of the layers of electrochromic material can reversibly insert cations and electrons, the modification of their degree of oxidation following these insertions /ariesinsertions leading to a change in its optical and / or thermal properties.
• the electrolyte in the form of a polymer or a gel; for example a proton-conductive polymer such as those described in patents EP-253 713 or EP-670 346, or a conductive polymer of lithium ions such as those described in patents EP-382 623, EP-518 754 and 532,408; the other layers of the system are generally of a mineral nature,
• all-polymer a category often referred to as the "all-polymer" system.
• the present invention is concerned with electrochromics "all solid" All these systems have in common the need to be equipped with current leads supplying electroconductive layers on either side of the layer or the various activated layers). system.
• the laminated assembly common in the automotive field, is only possible with substantially flat substrates and with a limited number of substrates (2 or 3). It is almost impossible with strongly curved substrates, especially when their number is greater than 2 or even 3 and generally leads to the risk of optical distortion.
• the present invention therefore aims to overcome the solutions of the prior art by proposing a system controllable by a single power supply and whose operating performance is at least identical to that of two juxtaposed systems.
• the subject of the invention is an electrochemical / electrically controllable device, with optical and / or variable energy properties of the "all solid" electrochromic type of structure TC1 / EC1 / EL / EC2 / TC2, comprising at least one carrier substrate provided with a first electroconductive layer, a first electrochemically active layer capable of reversibly inserting ions such as H +, Li + cations or anions such as OH-, in particular into an anodic (or cathodic) electrochromic material, an electrolytic layer, a second electrochemically active layer capable of reversibly inserting said ions, in particular of a cathodic (or anodic) electrochromic material, a second electroconductive layer, characterized in that at least one of the electrochemically active layers capable of inserting reversible said ions, in particular an anodic electrochromic material cathode has a sufficient thickness so as to allow insertion of all the ions without electrochemical dysfunction of said active layers, and in that the
• the thickness of the layer EC2 is between 400 and 150O nm and preferably between 700 nm and 1300 nm, and even more preferably between SOO and 1200 nm,
• the electroconductive layer TC1 or TC2 is of the metallic type or of the TCO (Transparent Conductive Oxide) type in InaCtoSn (ITO), SnO2: F, ZnO: A1, or is a multi-layer of the TCO / type; metal f TCO ? this metal being chosen in particular from silver, gold, platinum, copper, or a NiCr / metal / NiCr type multi-layer, the metal being also chosen in particular from silver, gold, platinum; , the copper, the contrasts obtained are between 9 to 10,000 and preferably between 15 to 4000.
• TCO Transparent Conductive Oxide
• electrochromic glazing which is characterized in that it comprises the electrochemical device according to one of the preceding claims, in particular having a transmission and / or light reflection and / or variable energy, with the substrate or at least a part of the transparent (or partially transparent) substrates, made of plastic material, preferably mounted in multiple glazing and / or laminated, or in double glazing.
• it relates to a method for manufacturing the electrochemical device, as previously described, in which at least one of the layers of the electrochemical device is deposited by a technique using vacuum, of the cathode sputtering type, possibly assisted.
• glazing especially of toughened type, spray-coating or laminar coating.
• the term “lower” electrode means the electrode which is closest to the carrier substrate taken as reference, on which at least part of the active layers (for example all the active layers in a electrochromic system “all solid") is deposited.
• the “upper” electrode is the one deposited on the other.
• the electrode remains transparent, that is, it has low light absorption in the visible.
• it is not excluded to have much thicker layers (especially in the case where the electro-chromatic electroactive system operates in reflection rather than transmission), or thinner layers (especially when they are associated in the electrode to another type of conductive layer, metal for example).
• the invention can be applied to different types of electrochemical or electro-controllable systems.
• the electrochromic systems or glazing to which the invention can be applied are described in the aforementioned patents. They may comprise at least two carrier substrates between which are included stacks of functional layers each comprising at least successively a first electroconductive layer, an electrochemically active layer capable of reversibly inserting ions such as H +, Li + , OH- of the type an anodic or cathodic electrochromic material, an electrolyte layer, a second electrochemically active layer capable of reversibly inserting ions such as H + , Li + , OH " of the cathodic or anodic electrochromic material type, and a second electroconductive layer, term "layer” is to be understood as a single layer or a superposition of several layers, continuous or discontinuous.
• the invention also relates to the incorporation of the electrochemical devices described in the preamble of the present application in glazings, operating in reflection (mirror) or transmission.
• the term "glazing” is to be understood in the broad sense and includes any substantially transparent material, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA).
• the carrier substrates and / or counter-substrates that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible.
• This glazing can be used as glazing for the building, glazing for the automobile, glazing of industrial vehicles or public transport, railway, maritime, air, in particular porthole, mirrors, mirrors.
• This glazing having in particular a transmission and / or light reflection and / or variable energy, with the substrate or at least a portion of the transparent or partially transparent substrates (s), plastic material or glass, is preferably mounted in multiple glazing and / or laminated, or double glazing.
• the invention also relates to the various applications that can be found in these devices, glazing or mirrors: it may be to make glazing for building, including external glazing, internal partitions or glass doors). It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats. It can also be display or display screens, such as projection screens, television or computer screens, touch screens, commonly known in English.
• Display They can also be used to make glasses or camera lenses, or to protect solar panels.
• FIG. 1 a schematic view of an electrochromic cell according to the invention
• Figure 2 shows a schematic cross section of Figure 1.
• Figure 2 is intentionally highly schematic and not necessarily to scale for ease of reading: it shows in section an electrochromic device "all solid ⁇ according to the teachings of the invention comprising successively:
• a lower electroconductive layer 2 comprising a stack of layers of the ITO / ZnO type: Ai / Ag / ZnO: A1 / ITO respective thicknesses 15 to 20 nm for 11TO / 60 at SO nr ⁇ for ZnO: Al / 3 at 15 nm for silver / 60 to 80 nm for ZnO: Al / 15 at 20 nm for TITO, or di-oxide base (doped tin oxide to tin) of 500 nm, deposited hot - a first electrochromic system 3 whose structure will be described below
• a preferred embodiment of this type of electroconductive layer is to apply on the dlTO layer (optionally surmounted by one or more other conductive layers) a plurality of conductive strips, or a network of conductive son 6 embedded on the surface of a polymer sheet 7 as a lamination interlayer and for electrically supplying the upper electroconductive layer associated with the electrochromic stack.
• Electrochrome 3 comprises:
• a first layer of anodic electrochromic material EC1 in iridium oxide (hydrated) of 70 nm to 250 nm or of hydrated nickel oxide of 200 to 400 nm, alloyed or not with other metals (alternatively, layer can be replaced by a layer of anodic electrochromic material in nickel oxide of 200 to 400 nm, allied or not with other metals)
• tungsten oxide of 100 nm a layer of tungsten oxide of 100 nm, a second layer of hydrated tantalum oxide or of hydrated silica oxide or of hydrated zirconium oxide of 100 nm, the latter two layers forming an electrolyte-functional layer EL; a second layer of cathodic EC2 electrochromic material; The entire set of layers was deposited by magnetic field assisted sputtering using a tungsten oxide WO3 of 400 to 1200 nm.
• the active stack 3 may be incised on all or part of its periphery grooves made by mechanical means or by laser radiation attack, possibly pulsed, and this, to limit peripheral electrical leakage as described in the French application FR-2 781 084.
• the glazing shown in FIGS. 1, 2 incorporates (not shown in the figures) a first peripheral seal in contact with the faces 2 and 3 (2 and 3 being in a conventional manner the numbering of the internal faces of the substrates Sl and S2), 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 faces 1 and 4 (1 and 4 being in a conventional manner the numbering of the external faces of substrates S1 and S2), so as to provide: a barrier, a mounting means with the means of transport, a seal between the inside and the outside, an aesthetic function, means for incorporating reinforcement elements.
• the electrochromic device described above constitutes Example 1.
• the electrochromic device of this example 1 has been connected to a energy source so as to allow switching between a colored state and a discolored state and vice versa.
• the association, on a silico-sodo-calcic substrate coated with ITO with an overall thickness of 2.1 mm, includes an electrochromic system comprising:
• this layer having an electrolyte function EL
• a second layer of cathodic electrochromic material EC2 based on tungsten oxide WO 3 of 350 to 390 nm, preferably 380 nm, allows switching of the glazing between a bleached state characterized by a light transmission (TL) of 55% and a state of colored characterized by a TL of 2.5%.
• the contrast associated with this glazing is 22 for a quantity of exchanged charges of 25 to 30 mC / cml
• the measurement of the quantity of charges circulating during the discoloration / discoloration cycles between the electroactive layers corresponds to a number of charges per unit of stacking surface, normalized to a given active layer thickness and increasing linearly with the thickness of said layer.
• a second layer of hydrated tantalum oxide this layer having an electrolyte function EL, a second layer of cathodic electro chromium material EC2 based on tungsten oxide WO3 of 400 to 600 nm, preferentially 500 nm, makes it possible to switch the glazing between a discolored state characterized by a light transmission (TL) of 50% and a colored state characterized by a TL of 1%.
• the contrast associated with this glazing is 50 for a quantity of exchanged charges of 33 to 40 mC / cm 2 .
• this layer having an electrolytic function EL
• the contrast associated with this glazing is 4000 for a quantity of exchanged charges of 66 to 80 mC / cm. 2 . If we compare Examples 2 and 3 to Example 1, we can notice that as soon as the thickness of the EC2 layer is significantly increased, it is possible to obtain high contrast values, while retaining a quantity of charges exchanged substantially in the same order of magnitude.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Nonlinear Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
• Joining Of Glass To Other Materials (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 2006
  • 2006-08-04 FR FR0653294A patent/FR2904704B1/fr active Active
• 2007
  • 2007-07-26 EA EA200970179A patent/EA014682B1/ru not_active IP Right Cessation
  • 2007-07-26 US US12/375,045 patent/US7894120B2/en active Active
  • 2007-07-26 JP JP2009522313A patent/JP5247695B2/ja active Active
  • 2007-07-26 CN CN2007800291452A patent/CN101501562B/zh active Active
  • 2007-07-26 WO PCT/FR2007/051729 patent/WO2008017777A2/fr active Application Filing
  • 2007-07-26 EP EP07823645A patent/EP2047326A2/de not_active Withdrawn
  • 2007-07-26 KR KR1020097002154A patent/KR20090034948A/ko active IP Right Grant
  • 2007-07-26 BR BRPI0714922-0A patent/BRPI0714922A2/pt not_active IP Right Cessation
  • 2007-07-26 CA CA002659614A patent/CA2659614A1/fr not_active Abandoned

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