WO2019030269A1 - Compositions comprising dispersed nanoparticles of electrochromic oxide - Google Patents

Compositions comprising dispersed nanoparticles of electrochromic oxide Download PDF

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Publication number
WO2019030269A1
WO2019030269A1 PCT/EP2018/071480 EP2018071480W WO2019030269A1 WO 2019030269 A1 WO2019030269 A1 WO 2019030269A1 EP 2018071480 W EP2018071480 W EP 2018071480W WO 2019030269 A1 WO2019030269 A1 WO 2019030269A1
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solid substrate
layer
lithium
group
composite layer
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PCT/EP2018/071480
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French (fr)
Inventor
Michael Goebel
Ralf Noerenberg
Jens Roeder
Fabian Seeler
Garo Khanarian
Erich Beck
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Basf Se
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    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2258—Oxides; Hydroxides of metals of tungsten
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or Groups 11 to 13 of the Periodic system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements

Definitions

  • compositions comprising dispersed nanoparticles of electrochromic oxide
  • the present invention relates to compositions (also referred to as inks) comprising nanoobjects and to a process for preparing a layer comprising nanoobjects on a surface of a solid substrate.
  • Electronic devices e.g. optoelectronic devices or electrochromic devices often contain functional layers comprising nanoobjects, e.g. nanoobjects comprising an electrochromic material.
  • Such functional layers are commonly prepared by wet processing techniques wherein a liquid composition (commonly referred to as an "ink") comprising suspended nanoobjects is applied to a surface of a solid substrate.
  • a liquid composition commonly referred to as an "ink”
  • Compositions comprising suspended nanoobjects are also used for preparing any other objects and formulations comprising nanoobjects.
  • WO 2016/128133 A1 proposes addition of dispersing agents in the form of metal salts to inks comprising nanoobjects.
  • Preferred salts are formiates, acetates, citrates, oxalates, nitrates and halogenides of metal cations from the group consisting of Zn, Al, Y, Pb, Bi Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Mg, Ca, Sr and Ba.
  • Related art is also
  • compositions comprising dispersed nanoobjects wherein agglomeration and/or settling of said nanoobjects is effectively suppressed over a long duration, even in case of a high concentration and/or small size of said dispersed nanoobjects.
  • composition comprising
  • a composition according to the present invention is in the form of a suspension, also referred to as slurry.
  • a suspension also referred to as slurry.
  • such composition is also referred to as an ink.
  • Preparation of suspensions is known in the art.
  • the term "suspension” denotes a dispersion comprising a continuous phase (in the literature sometimes referred to as an external phase e.p.) that is liquid and at least one dispersed phase (in the literature sometimes referred to as an internal phase i.p.) that is solid and does not dissolve in said continuous phase which is liquid.
  • the nanoobjects (a) form a dispersed phase, which is dispersed within the liquid external phase.
  • the external liquid phase consists of the above- defined liquid constituents (b), (c) and (g) and any constituents which are dissolved in said liquids.
  • Said nanoobjects (a) comprise one or more electrochromic oxides of tungsten.
  • said nanoobjects (a) consist of one or more oxides of tungsten.
  • nanoobject refers to an object having one, two or three external dimensions in the nanoscale, i.e. in the size range from approximately 1 nm to 100 nm.
  • nanoplates Said one external dimension in the nanoscale corresponds to the thickness of the nanoplate.
  • the two significantly larger dimensions differ from the nanoscale dimension by more than three times.
  • the two larger external dimensions are not necessarily in the nanoscale.
  • Another common term for denoting a nanoobject having one external dimension in the nanoscale, while the other two external dimensions are significantly larger, is "nanoflake”.
  • nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension is significantly larger are generally re- ferred to as nanofibers.
  • the third significantly larger dimension differs from the nanoscale dimensions by more than three times.
  • the largest external dimension is not necessarily in the nanoscale.
  • Said largest external dimension corresponds to the length of the nanofibers.
  • Nanofibers typically have a cross section close to circular shape. Said cross section extends perpendicularly to the length. Said two external dimensions which are in the nanoscale are defined by the diameter of said circular cross section.
  • Electrically conductive nanofibers are also referred to as nanowires. Hollow nanofibers (irrespective of their electrical conductivity) are also referred to as nanotubes.
  • Nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension (length) is significantly larger, which are rigid (i.e. not flexible) are commonly referred to as nanorods.
  • Nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension (length) is significantly larger, and have a cross section close to rectangular shape extending perpendicularly to the length, are commonly referred to as nanoribbons.
  • nanoobjects having all three external dimensions in the nanoscale wherein the length of the longest axis and the length of the shortest axis of the nanoobject differ not significantly, are generally referred to as nanoparticles.
  • the length of the longest axis and the length of the shortest axis differ by not more than three times.
  • nano- spheres Approximately isometric nanoparticles, i.e. the aspect ratio (longest : shortest direction) of all three orthogonal external dimensions is close to 1 , are commonly referred to as nano- spheres.
  • the nanoobjects of constituent (a) of the present invention are nanoparticles.
  • Preferred nanoparticles are approximately isometric, i.e. the aspect ratio (longest : shortest direction) of all 3 orthogonal external dimensions is in the range of from 1 to 2.
  • Especially preferred nanoparticles are nanospheres.
  • nanoparticles are primary particles having a primary particle diameter of 1 nm to 100 nm, preferably 3 nm to 50 nm (measured by nitrogen absorption, X-ray diffraction or transmission electron microscopy). Preferred are nanoparticles having a primary particle diameter of less than 20 nm, more preferably less than 15 nm, further preferably 12 nm or less. According to DIN 53206-1 : 1972-08, the term "primary particles" refers to entities which are discernible as individuals by means of optical microscopy or transmis- sion electron microscopy.
  • the nanoobjects are nanoparticles which in suspension have a hydrody- namic size D90 of less than 100 nm (measured by dynamic light scattering or centrifugal sedimentation techniques).
  • Electrochromic materials are characterized by an ability to change their optical properties, reversibly, and persistently, when a voltage is applied across them (see Claes G. Granqvist, Solar Energy Materials & Solar Cells 99 (2012) 1-13). This ability is herein also referred to as the "electrochromic effect".
  • a change of the optical absorption of the electrochromic material occurs when electrons are transferred to or away from the electrochromic material, along with charge balancing ions entering from an adjacent electrolyte.
  • Certain electro- chromic materials have the property of exhibiting a change, evocation, or bleaching of color (in the visible range of the electromagnetic spectrum) as effected either by an electron- transfer (redox) process or by a sufficient electrochemical potential (see Mortimer, R.
  • Electrochromic metal oxides are known in the art, see e.g. Mortimer, R. J.: “Electrochromic materials”, Annu. Rev. Mater. Res. 201 1 . 41 :241-68 and Granqvist, C. G.: “Oxide electro- chromics: An introduction to devices and materials", Solar Energy Materials & Solar Cells 99 (2012) 1-13.
  • Oxides of tungsten are known to have an electrochromic effect.
  • Tungsten oxide WO3 which is virtually colorless colors blue during cathodic reduction in combination with simultaneous intercalation of charge-balancing cations M (typically one of H + , Li + , Na + , K + ) thus forming MxW03.
  • M charge-balancing cations
  • nanoobjects (a) comprising one or more electrochromic oxides of tungsten is known in the art.
  • said nanoobjects (a) are nanoparticles synthesized by a gas phase pyrolysis process, preferably flame spray synthesis. Such nanoparticles are commercially available.
  • Constituent (b) of the composition according to the invention is water.
  • Constituent (c) of the composition according to the invention is an organic liquid having a boiling point of less than 120 °C.
  • the boiling point refers to the standard pressure of 101 .325 kPa.
  • Constituents (b) and (c) form a carrier liquid having a boiling point below 120 °C.
  • Said carrier liquid is merely a vehicle for wet processing and usually does not remain in the layer to be formed from the above-defined composition.
  • said organic liquid having a boiling point below 120 °C (c) has a polarity index > 4 according to the polarity scale, based on the polarity index of water being 9 (V.J. Barwick, Trends in Analytical Chemistry, vol. 16, no. 6, 1997, p.293ff, Table 5).
  • Said organic liquid having a boiling point below 120 °C is not polymerizable.
  • said organic liquid having a boiling point below 120 °C is selected from the group consisting of alcohols, amines, carbonic acids, esters, ketones, organic carbonates, poly- ethers, sulfides and nitriles and mixtures thereof.
  • said organic liquid hav- ing a boiling point below 120 °C is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert.-butanol, 2-butanone, 2-pen- tanone, methyl isobutyl ketone, dimethyl carbonate, ethyl methyl carbonate, 1 ,2-dimethoxy- ethane, acetonitrile, pyridine, propionitrile, dimethylamine, formic acid, acetic acid, ethyl acetate, dimethoxyethane, acetone, dimethyl carbonate, dioxane, trifluoromethyl methyl carbonate, ethyl methyl carbonate, 2-methyltetrahydrofuran, chloroform and mixtures thereof.
  • Especially preferred ones are selected from the group consisting of ethanol, methanol, 2-propanol,
  • a composition according to the invention may be used as an ink for preparing an electro- chromic layer. For further details, see below.
  • a composition according to the invention further comprises
  • polymerizable moieties as used herein includes polymerizable monomers and polymerizable oligomers. Said polymerizable moieties (d) are dissolved in the liquid phase of the composition.
  • Said polymerizable moieties (d) are precursors of a polymer matrix.
  • said polymerizable moieties form a polymer matrix by polymerization on a surface of a solid substrate to which the above- defined composition has been applied.
  • said matrix binds and accommodates the nanoobjects (a) and optionally further constituents (see below) within said layer, fills the voids between said nanoobjects (a), provides mechanical integrity and stability to the layer and binds the layer to the surface of the solid substrate.
  • said polymerizable moieties are selected from the group consisting of alkyl acrylates, alkyl methacrylates, hydroxyalkyi acrylates, hydroxyalkyi methacrylates, vinyl chloride, vinyl fluoride, acrylonitrile, vinylidene fluoride, vinylidene chloride, hexafluoropropyl- ene, trifluoroethylene, tetrafluoroethylene, tetrahydrofurane, vinylpyrrolidone, polyisocya- nates in combination with polyols and/or diamines.
  • said polymerizable moieties are co-polymerizable monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and from the group consisting of hydroxyalkyi acrylates and hydroxyalkyi methacrylates.
  • the molar ratio between the total amount of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and the total amount of monomers selected from the group of hydroxyalkyi acrylates and hydroxyalkyi methacrylates is in the range of from 0.0002 to 50000, preferably 0.4 to 200.
  • said polymerizable monomers are butyl acrylate and hydroxybutyl acrylate.
  • composition preferably further comprises
  • Suitable initiators are known in the art and commercially available.
  • said initiators are selected from the group consisting of compounds which decompose into radicals when exposed to electromagnetic irradiation.
  • a composition according to the invention further comprises
  • the polymers (f) are either dissolved in the liquid external phase of the composition, or -in case they are not soluble in said liquid phase- they are present in the form of particles which are suspended within said liquid phase.
  • said polymers (f) are selected from the group consisting of polyalkyl acrylates, polyalkyl methacrylates, polyhydroxyalkyl acrylates, polyhydroxyalkyl methacrylates, polyvinyl chloride, polyvinyl fluoride, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polyhexafluoropropylene, polytrifluorethylene, polytetrafluoroethylene, polytetra- hydrofuran, polyvinylpyrrolidone, polyurethanes, polyethylene oxides.
  • composition according to the invention further comprises
  • the boiling point refers to the standard pressure of 101.325 kPa.
  • said aprotic organic liquid (g) is mixed with the carrier liquid so that a common liquid phase exists in the above-defined composition. Accordingly, the organic liquid (c) having a boiling point below 120 °C and the aprotic organic liquid (g) having a boiling point of 120 °C or higher are selected to be mis- proficient with water (constituent (b)).
  • Said aprotic organic liquid is selected to have a boiling point of 120 °C or higher, in order to allow said aprotic organic liquid (g) to remain in a layer prepared from the above-defined composition, when heat is applied during the steps of removing the carrier liquid and poly- merizing the polymerizable moieties.
  • Said aprotic organic liquid (g) is not polymerizable.
  • Said aprotic organic liquid (g) is selected to be capable of allowing for dissolution and dissociation of at least one electrolyte (h) as defined below.
  • said aprotic organic liquid (g) is selected from the group consisting of organic carbonates, alcoholes, amides, carboxylic acid esters, ethers, polyethers, ketones, lactones, lactames, phosphoric acid esters, sulfones, sulfoxides, sulfonates, urea, thiourea, derivatives of urea resp. thiourea, and mixtures thereof.
  • Derivatives of urea resp. thiourea are compounds wherein one or more of the hydrogen atoms of urea resp.
  • thiourea are substituted. Examples are ethylene urea (2-lmidazolidon) ⁇ , ⁇ '-dimethylpropylene urea, N- (2-hydroxyethyl)ethylene urea and the corresponding thiourea derivatives.
  • said aprotic organic liquid (g) is selected from the group consisting of ethylene carbonate, 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, 1 ,2-butylene carbonate, 1 ,3-butylene carbonate, 1 ,4-butylene carbonate, 2,3-butylene carbonate, ethylene glycol, diethylene glycol, diethyl carbonate, gamma-butyrolactone, gamma-valerolactone, sulfolane, dimethyl sulfoxide, 1 ,3-deimethyl-3,4,5,6-tetrahydro-2(1 H)-pyrimidinone (DMPU) and mixtures thereof.
  • DMPU dimethyl sulfoxide
  • ethylene carbonate fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3- propylene carbonate and mixtures thereof.
  • composition according to the invention further comprises
  • electrolyte having cations selected from the group consisting of H + , Li + , Na + and K + .
  • electrolyte is known in the art and denotes a substance which is capable of dissociating into mobile ions.
  • said electrolyte (h) dissolved in said aprotic organic liquid (g) provides ionic conductivity.
  • said composition does not comprise any salts which are not selected from the group of electrolytes comprising at least one cation from the group consisting of H + , Li + , Na + and K +
  • water does not belong to the electrolytes (h) as defined above. Accordingly, said electrolyte comprises at least one anion which is different from OH " or at least one cation from the group consisting of Li + , Na + and K + .
  • Preferred electrolytes (h) are lithium salts.
  • said at least one electrolyte (h) is selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide.
  • Said electronically conductive nanoobjects (i) form a dispersed phase, which is dispersed within the liquid external phase of the composition according to the present invention.
  • said electronically conductive nanoobjects deposited on a surface of a solid substrate may form a conductive network of adjacent and overlapping electronically conductive nanoobjects capable of carrying an electric current.
  • said electroconductive nanoobjects (i) have two external dimensions in the range of from 1 nm to 100 nm, and their third external dimension is in the range of from 1 ⁇ to 100 ⁇ , in each case determined by transmission electron microscopy.
  • said two external dimensions which are in the range of from 1 nm to 100 nm are similar i.e. they differ in size by less than three times.
  • the third dimension of said electroconductive nanoobjects is significantly larger, i.e. it differs from the other two external dimensions by more than three times.
  • said electroconductive nanoobjects (i) are nanowires as defined in ISO TS 27687:2008 (as published in 2008) (for details, see above).
  • the electronically conductive nanoobjects (i) are nanowires having a length in the range of from 1 ⁇ to 100 ⁇ , preferably of from 3 ⁇ to 50 ⁇ , more preferably of from 10 ⁇ to 50 ⁇ , and a diameter in the range of from 1 nm to 100 nm, preferably of from 2 nm to 50 nm, more preferably of from 15 nm to 30 nm, length and diameter in each case being determined by transmission electron microscopy.
  • said electronically conductive nanoobjects are nanowires comprising materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel. More preferably, said electronically conductive nanoobjects are nanowires consisting of materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel.
  • Compositions according to the invention which comprise the above-defined constituents (h) and (i) are preferably obtained by a method following the teaching of non-prepublished patent application having the application number PCT/EP2017/055320.
  • said method comprises providing a first suspension comprising above-defined constituents (a), and at least one of (b) and (c), providing a second suspension comprising above-defined constituents (i), and at least one of (b) and (c) (with the proviso that at least one of the first and the second suspension contains constituent (b) and at least one of the first and the second suspension contains constituent (c), adding together said first suspension and said second suspension to obtain a third suspension comprising above-defined constituents (a), (b), (c), and (i), and admixing to said third suspension the above-defined constituents (d), (g), (h) and optionally (e) and (f).
  • a composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d) and (g) and optionally one, more or all of the above-defined constituents (e), (f), (h) and (i) contains a single continuous liquid phase comprising the constituents (b), (c) and (g) which at standard pressure 101.325 kPa are liquid at temperatures below 120 °C and constituent (d) and - if present - constituent (e) and constituent (f) (if present in the form of soluble polymers) which are dissolved in said liquid phase.
  • Constituents (a) and - if present - constituent (i) and constituent (f) each form a dispersed phase, which is dispersed within the liquid external phase.
  • a composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d), (g) and (h) and optionally one, more or all of the above-defined constituents (e), (f), and (i) may be used for preparing an electrochromic composite layer which in an electrochromic device can function as an electrochromic electrode.
  • An electrochromic composite layer obtainable from a composition which contains the above-defined constituents (a), (b), (c), (d), (g), (h) and optionally one, more or all of the above-defined constituents (e), (f) and (i), comprises
  • an electrochromic composite layer as defined above further comprises (i) electronically conductive nanoobjects not comprising any oxides of tungsten dispersed within said matrix formed of one or more organic polymers.
  • electrochromic composite layer denotes a layer comprising discrete nanoobjects (a) comprising one or more electrochromic oxides of tungsten as defined above and constituents (g), (h) and optionally (i) dispersed within a continuous phase (matrix) extending throughout said layer.
  • a discrete nanoobjects
  • constituents g
  • h constituents
  • i dispersed within a continuous phase (matrix) extending throughout said layer.
  • an electronically conductive network and an ionically conductive network extend throughout the electrochromic composite layer providing for the transport of electrons and ions to and away from the dispersed nanoobjects comprising electrochromic compounds as defined above.
  • Further constituents may be dispersed in the matrix, each fulfilling a specific function and interacting with the other constituents.
  • the matrix provides mechanical integrity and stability and binds and accommodates the above-defined constituents of the electrochromic composite layer which are dispersed within said matrix.
  • the nanoobjects (a) comprising one or more electrochromic oxides of tungsten as defined above and -if present - the electronically conductive nanoobjects (i) as defined above, which are dispersed within the matrix, form a network extending throughout the electrochromic composite layer providing for the transport of electrons towards and away from the nanoobjects (a).
  • aprotic organic liquid (g) including said dissolved electrolyte (h) as defined above is confined within pores extending through the matrix, thus providing a network for the transport of ions to and away from the nanoobjects (a).
  • Water may also provide for ionic conductivity of the electrochromic composite layer.
  • the amount of water that remains in said system consisting of water (b) and two other liquids (c) and (g) as defined above can be estimated according to Raoult's law or can be determined from experimental data, as known by the skilled person. However, in the context of this disclosure, water is not an electrolyte (h) as defined above.
  • a composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d) and (g) and optionally one, more or all of the above-defined constituents (e), (f), and (i) may be used for preparing a precursor layer of an electrochromic composite layer.
  • a precursor layer of an electrochromic composite layer differs from an electrochromic composite layer as defined above in that said precursor layer does not contain any electrolytes (h).
  • a precursor layer of an electrochromic composite layer may be transferred into an electrochromic composite layer by allowing migration or diffusion of ions of an electrolyte (h) as defined above from another source (see below) into said precursor layer.
  • an electrochromic composite layer as defined above and a precursor layer thereof as defined above are herein commonly denoted as "a composite layer”.
  • a carrier liquid having a boiling point of less than 120 °C which does not become a constituent of the composite layer but merely acts as a vehicle for wet-processing.
  • a carrier liquid having a boiling point of less than 120 °C which does not become a constituent of the composite layer but merely acts as a vehicle for wet-processing.
  • the amount of nanoobjects comprising one or more electrochromic oxides of tungsten above is in the range of from 0.1 wt.-% to 20 wt.-%, preferably 0.5 wt.-% to 10 wt.-%,
  • the amount of water is in the range of from 0.04 wt.-% to 8 wt.-%, preferably 0.2 wt.- % to 4 wt.-%,
  • the amount of the organic liquid having a boiling point below 120 °C is in the range of from 70 wt.-% to 99.5 wt.-%, preferably 88 wt.-% to 99 wt.-%,
  • the total amount of polymerizable moieties is in the range of from 0.0005 wt.-% to 4.9 wt.-%, preferably 0.025 wt.-% to 1.04 wt.-%,
  • the total amount of initiators (if present) is in the range of from 0.00001 wt.-% to 0.06 wt.-%, preferably 0.0001 wt.-% to 0.02 wt.-%,
  • the total amount of said polymers is in the range of from 0 wt.-% to 4.9 wt.-%, preferably 0.025 wt.-% to 1.04 wt.-%,
  • the amount of the aprotic organic liquid having a boiling point of 120 °C or higher is in the range of from 0.00009 wt.-% to 0.8 wt.-%, preferably 0.005 wt.-% to 0.7 wt.%,
  • the total amount of said electrolytes as defined above is in the range of from 0 wt.- % to 0.3 wt.-%, preferably 0 wt.-% to 0.075 wt.-%,
  • the total amount of electronically conductive nanoobjects as defined above is in the range of from 0 wt.-% to 0.9 wt.-%, preferably 0 wt.-% to 0.4 wt.-%,
  • the total amount of monomers selected from the group consisting of alkyi acrylates and alkyi methacrylates is in the range of from 0.0004 wt.-% to 4.0 wt.-%, preferably 0.02 wt.-% to 0.84 wt.-%, and the total amount of monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates is in the range of from 0.0001 wt.-% to 0.9 wt.-%, preferably 0.005 wt.-% to 0.2 wt.- %.
  • the amount of electronically conductive nanoobjects (i) may be not sufficient to have a remarkable effect on the electronic conductivity.
  • the amount of nanoobjects (a) comprising one or more oxides of tungsten as defined above may be not sufficient for achieving an appropriate electrochromic effect.
  • an electrochromic composite layer prepared from a composition according to the invention the amount of electrolytes (h) may be not sufficient for achieving an appropriate ionic conductivity.
  • the amount of nanoobjects (a) comprising one or more oxides of tungsten as defined above may be not sufficient for achieving an appropriate electrochromic effect.
  • the amount of the aprotic organic liquid (g) in an electrochromic composite layer prepared from a composition according to the invention may be not sufficient for dissolving the electrolytes (h).
  • the amount of electrolytes (h) in an electrochromic composite layer prepared from a composition according to the invention may be not sufficient to achieve an appropriate ionic conductivity if there is no migration or diffusion of ions of an electrolyte (h) as defined above from another source into said layer.
  • said electronically conductive nanoobjects as defined above is in the range of from 0.00002 to 49, preferably 0.018 to 2.06.
  • the amount of polymerizable moieties in the composition may be not sufficient for forming a matrix which is capable of binding and accommodating the constituents (a), (g), (h) and (i) as described above when an electrochromic composite layer is prepared from a composition according to the invention.
  • the amount of the constituents (a), (g), (h) and (i), which determine the electrochromic effect and other important properties of an electrochromic composite layer prepared from a composition according to the present invention may be not sufficient to achieve the desired properties.
  • the total weight of nanoobjects comprising one or more oxides of tungsten is in the range of from 3.5 to 1075, preferably 8.8 to 206.
  • the fraction of solids in the composition is quite high, which may impede application of the composition by means of wet processing techniques.
  • the fraction of the carrier liquid, which has to be removed in the process of forming an electrochromic composite layer is relatively large, and processing may become inefficient.
  • the fraction of water in the carrier liquid is quite low and may be not sufficient to achieve the desired effect.
  • the fraction of said organic liquid having a boiling point below 120 °C in the carrier liquid is quite low and may be not sufficient to achieve the desired effect
  • said nanoobjects are nanoparticles comprising one or more oxides of tungsten, preferably consisting of one or more oxides of tungsten
  • said organic liquid having a boiling point below 120 °C is selected from the group consisting of ethanol, methanol, 2-propanol, 2-methyl tetrahydrofuran and mixtures thereof
  • said polymerizable moieties are one or more kinds of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more kinds of monomers selected from the group consisting of hydroxyalkyl acrylates and hydrox- yalkyl methacrylates
  • said initiator is an initiator which decomposes into radicals when exposed to irradiation
  • said aprotic organic liquid is selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2- propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
  • said at least one electrolyte is selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sulfonimide and lithium bis(fluorosulfonyl)imide
  • said electronically conductive nanoobjects are nanowires comprising, preferably consisting of materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel, preferably silver nanowires.
  • composition according to the present invention further comprises
  • polymerizable monomers are butyl acrylate and hydroxybutyl acrylate.
  • a second aspect of the present invention relates to a process for preparing a composite layer as defined above on a surface of a solid substrate
  • composition applied to said surface of said solid substrate comprises
  • preparing said process further comprises the step of annealing the layer formed on the surface of the solid substrate after polymerizing the polymerizable monomers.
  • Said solid substrate comprises, preferably consists of, one or more materials selected from the group consisting of glasses, metals, transparent conducting oxides and organic poly- mers.
  • the surface of the solid substrate to which the composition according to the invention is applied comprises an electronically conductive material, preferably an optically transparent electronically conductive material.
  • Preferred optically transparent conducting materials are transparent conducting oxides (TCO), preferably selected from the group consisting of ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), IGZO (indium gallium doped zinc oxide), GZO (gallium doped zinc oxide), FTO (fluorine doped tin oxide), indium oxide, tin oxide and zinc oxide.
  • TCO transparent conducting oxides
  • the surface of the solid substrate layer upon which the electrochromic composite layer is arranged comprises one or more metallic electronically conductive materials, wherein the metals are preferably se- lected from the group consisting of Cu, Ag, Au, Pt and Pd.
  • the metal at the solid substrate surface is present in the form of a structure which is optically transparent, e.g. in the form of fine mesh or nanowires.
  • the composition comprises electroconduc- tive nanoobjects (i) as defined above
  • the electronic in-plane conductivity of an electro- chromic composite layer prepared from a composition according to the invention is sufficiently high so that providing the solid substrate surface with an electronically conductive material can be omitted.
  • Said solid substrate is preferably in a form selected from the group consisting of foils, films, webs, panes and plates.
  • said solid substrate comprises an organic polymer and has a thickness the range of from 10 ⁇ to 200 ⁇ , preferably from 50 ⁇ to 150 ⁇ .
  • said solid substrate comprises glass and has a thickness in the range from 3 to 7 mm, preferably 4 to 6 mm, or in the range from 0.5 to 2.5 mm, preferably 0.7 to 2 mm.
  • Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass.
  • the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing away from the above- described composite layer.
  • Preferred organic polymers are selected from the group consisting of polymethylmethacrylate (PMMA, commercially available e.g. as PlexiglasTM), polycarbonate (PC), polyethylene (PE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP), polyethylene therephthalate (PET), glycol modified polyethylene therephthalate, polyethylene naphthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), polyvinyl chloride (PVC), polyimides (PI), pol- ypropyleneoxide (PPO) and mixtures thereof.
  • PET and PEN are particularly preferred.
  • said solid substrate has a light transmission of 80 % or more measured according to ASTM D1003 (Procedure A) as published in November 2013.
  • the composition according to the present invention is applied to the surface of said solid substrate by coating or printing, preferably by a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultra- sonic spray-, dip- and blade coating, or by a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing.
  • a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultra- sonic spray-, dip- and blade coating
  • a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing.
  • the wet film formed by applying the composition according to the present invention to said surface of said solid substrate has a thickness in a range of from 1 ⁇ to 250 ⁇ , preferably of from 20 ⁇ to 150 ⁇ . Said thickness is also referred to as "wet thick- ness”.
  • the carrier liquid which has a boiling point below 120 °C is removed from said wet film on said surface of said solid substrate by exposing said wet film to a temperature in the range of from 20 °C to 120 °C, preferably 40 °C to 120 °C, most preferably 80 °C to 120 °C.
  • the composition which in the process according to the invention is applied to said surface of said solid substrate is selected from the above-defined preferred compositions according to the first aspect of the present invention.
  • the step of polymerizing the polymerizable moieties on said surface of said solid substrate is performed after the step of removing said carrier liquid having a boiling point below 120 °C from the wet film formed on said surface of said solid substrate.
  • the degree of conversation of the double bonds in the polymerizable moieties is significantly below 96 %, preferably 90 % or less, further preferably 80 % or less, more preferably 70 % or less, particularly preferably 60 % or less, or 50 % or less, and polymerization is completed in a later stage e.g. when the surface of the composite layer facing away from the solid substrate is to be bonded to another layer (see below).
  • An especially preferred process according to the second aspect of the present invention is a process for preparing a precursor layer of an electrochromic composite layer as defined above on a surface of a solid substrate, said process comprising the steps of
  • Another especially preferred process according to the second aspect of the present invention is a process for preparing an electrochromic composite layer as defined above on a surface of a solid substrate, said process comprising the steps of
  • the following constituents of the composition according to the first aspect of the present invention are applied to the surface of said solid substrate in the following amount per cm 2 of said surface:
  • nanoobjects comprising one or more oxides of tungsten as defined above in an amount of 0.05 mg/cm 2 to 2 mg/cm 2
  • (h) optionally electrolytes having cations selected from the group consisting of H + , Li + , Na + , K + in an amount of 0.000006 mg/cm 2 to 0.1 mg/cm 2
  • said polymerizable moieties are co-polymerizable monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and from the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates
  • said monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates are applied in an amount of 0.0006 mg/cm 2 to 10.9 mg/cm 2 and said monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates in an amount of 0.0001 mg cm 2 to 2.4 mg /cm 2 .
  • a third aspect of the present invention relates to the use of a composition according to the first aspect of the present invention for preparing a layer comprising a matrix formed of one or more kinds of organic polymers
  • (h) optionally at least one electrolyte having cations selected from the group consisting of H + , Li + , Na + and K + dissolved in said aprotic organic liquid (g) on a surface of a solid substrate.
  • the composition used herein is selected from the above-defined preferred compositions according to the first aspect of the present invention. It is noted that a composition according to the first aspect of the present invention may also be used for preparing any other objects and formulations comprising nanoobjects (a) as defined above.
  • a fourth aspect of the present invention relates to a process for preparing an article comprising a solid substrate having a surface and, arranged on said surface of said solid sub- strate, an electrochromic composite layer or a precursor layer thereof as defined above.
  • Said process comprises preparing a composite layer as defined above on a surface of a solid substrate by a process as described above in the context of the second aspect of the present invention.
  • said solid substrate comprises one or more materials selected from the group consisting of glasses, metals, transparent conducting oxides and organic polymers.
  • Said solid substrate is preferably in a form selected from the group consisting of foils, films, webs, panes and plates.
  • said solid substrate is optically transparent, i.e. exhibits a light transmission of 80 % or more measured according to DIN EN 410.
  • the above-defined layer is arranged on a surface of said solid substrate in such manner that it partially or completely covers a surface of said solid substrate. In specific cases the layer forms a pattern on said surface of said solid substrate.
  • the pattern may be selected from any random and non-random structures, like grids, stripes, waves, dots and circles.
  • the above-defined layer arranged on the surface of the solid substrate has a thickness in the range of from 0.05 ⁇ to 500 ⁇ , preferably 0.05 ⁇ to 50 ⁇ , most preferably 0.1 ⁇ to 30 ⁇ .
  • said composite layer comprises
  • nanoparticles comprising one or more oxides of tungsten, preferably consisting of one or more oxides of tungsten,
  • an aprotic organic liquid selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
  • (h) optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g).
  • electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g).
  • said composite layer further comprises
  • nanowires comprising, preferably consisting of, materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel
  • organic polymers which are copolymerization products of one or more monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates.
  • an article obtainable according to the fourth aspect of the present invention consists of the above-defined solid substrate and the above-defined layer arranged on a surface of said solid substrate.
  • an article obtainable according to the fourth aspect of the present invention contains further layers which may serve specific functions.
  • a specifically preferred article obtainable according to the fourth aspect of the present invention comprises a multilayer structure suitable for production of or use in an electrochromic device.
  • electrochromic device refers to a device exploiting the electrochromic effect as defined above. Such device comprises at least one elec- trode comprising an electrochromic material, a counter electrode and a separator layer sandwiched between and electronically separating said electrodes.
  • Electrochromic devices are used, inter alia, as fagade and roof elements, interior construction and design elements for buildings and vehicles, displays, visualization optics and electrochromic mirrors.
  • a widely known type of electrochromic devices are so-called smart windows.
  • smart windows is known in the art.
  • Such preferred article for production of or use in an electrochromic device comprises a first solid substrate having a surface
  • Such preferred article is obtainable by a process comprising the steps of
  • separator layer is virtually electronically insulating but allows for flow of ions.
  • Another preferred article for production of or use in an electrochromic device comprises a first solid substrate having a surface
  • a counter electrode layer arranged on said surface of said second solid substrate, a counter electrode layer a separator layer sandwiched between and electronically separating said composite layer and said counter electrode layer.
  • Said article comprises a multilayer structure which in the direction of stacking consists of a first solid substrate, a composite layer as defined above, a separator layer, a counter electrode layer and a second solid substrate.
  • said separator layer has a first surface and a second surface opposite to said first surface, wherein said first surface of said separator layer is in contact with a surface of said composite layer facing away from said first solid substrate, and said second surface of said separator layer is in contact with a surface of said counter electrode layer facing away from said second solid substrate.
  • Said separator layer is virtually electronically insulating and electronically separates the composite layer and the counter electrode but allows for flow of ions between the composite layer and the counter electrode. Suitable separator layers are known in the art.
  • Said separator layer preferably has a thickness in the range of from 0.05 ⁇ to 1500 ⁇ , preferably 0.05 ⁇ to 1000 ⁇ , most preferably 1 ⁇ to 800 ⁇ . Thickness may be determined by profilometry, atomic force microscopy or electron microscopy.
  • At least one of said solid substrates has a light transmission of 80 % or more measured according to DIN EN 410.
  • An article comprising the above-defined multilayer structure is obtainable by a process comprising the steps of
  • a first layer assembly comprising a first solid substrate having a surface and arranged on said surface of said first solid substrate a composite layer as defined above, and optionally a separator layer disposed on a surface of said composite layer facing away from said first solid substrate or a wet film obtained by applying a composition suitable for forming a separator layer on said surface of the first composite layer facing away from said first solid substrate, and
  • a second layer assembly comprising a second solid substrate having a surface and arranged on said surface of said second solid substrate a counter electrode layer, and optionally a separator layer disposed on a surface of said counter electrode layer facing away from said second solid substrate or a wet film obtained by applying a composition suitable for forming a separator layer on said surface of the counter electrode layer facing away from said second solid substrate,
  • At least one of said first and second layer assembly comprises a separator layer or a wet film as defined above
  • said separator layer comprises
  • disposing a separator layer on the surface of said composite layer facing away from said first solid substrate and/or on the surface of said counter electrode layer facing away from said second solid substrate preferably comprises the steps of forming on said surface of said composite layer resp. said counter electrode layer a wet film by applying to said surface a composition comprising
  • (c) optionally a carrier liquid having a boiling point below 120 °C
  • (h) optionally at least one electrolyte having cations selected from the group consisting of H + , Li + , Na + and K +
  • composition contains a carrier liquid (c") having a boiling point below 120 °C, removing the carrier liquid having a boiling point below 120 °C from the wet film formed on the surface of said composite layer resp. said counter electrode layer polymerizing the polymerizable moieties in the layer formed on the surface of said composite layer resp. said counter electrode layer.
  • a carrier liquid (c) having a boiling point below 120 °C removing the carrier liquid having a boiling point below 120 °C from the wet film formed on the surface of said composite layer resp.
  • said counter electrode layer polymerizing the polymerizable moieties in the layer formed on the surface of said composite layer resp. said counter electrode layer.
  • said composition for preparing the separator layer comprises a carrier liquid.
  • a carrier liquid as a vehicle for wet processing can be omitted, because said composition does not comprise non-dissolved matter, in contrast to the above-described composition for preparing an electrochromic composite layer or a precursor layer thereof. Accordingly, the step of removing the carrier liquid from the wet film can be omitted in preparing the separator layer.
  • carrier liquids c
  • polymerizable moieties d
  • initiators e
  • aprotic organic liquids g
  • electrolytes h
  • the polymerizable moieties (d") are the same as the polymerizable moieties (d) in the composition for preparing the composite layer
  • the aprotic organic liquid (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the composition for preparing the composite layer
  • - if present - the electrolyte (h") is the same as the electrolyte (h) in the composition for preparing the composite layer.
  • the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer and - if present - the electrolyte (h") is the same as the electrolyte (h) in the first composite layer.
  • aprotic organic liquid (g") including said dis- solved electrolytes (h") as defined above is confined within pores extending through the matrix, thus providing a network for the transport of ions across the separator layer.
  • Water may also provide for ionic conductivity of the separator layer.
  • a separator layer comprising water is obtainable by using a carrier liquid (c") consisting of water and another liquid having a boiling point of less than 120 °C.
  • the amount of water that remains in said system consisting of water and two other liquids can be estimated according to Raoult's law or can be determined from experimental data, as known by the skilled person.
  • water is not an electrolyte (h") as defined above.
  • the step of polymerizing the polymerizable moieties is performed after the step of removing said carrier liquid having a boiling point below 120 °C from the wet film formed on said surface of said solid substrate.
  • the degree of conversation of the double bonds in the polymerizable moieties is signif- icantly below 96 %, preferably 90 % or less, further preferably 80 % or less, more preferably 70 % or less, particularly preferably 60 % or less, or 50 % or less, and polymerization is completed in a later stage e.g. for bonding the surface of the separator layer facing away from the composite layer to another layer (see below).
  • composition forming a wet film by applying the above-defined composition on the surface of the layer wherein the polymerizable moieties have been polymerized, in case the composition contains a carrier liquid (c") removing from said wet film said carrier liquid having a boiling point below 120 °C,
  • the composition for preparing the separator layer is applied to the surface of said composite layer by coating or printing, preferably by a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultrasonic spray-, dip- and blade coating, or by a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing.
  • a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultrasonic spray-, dip- and blade coating
  • a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing.
  • the carrier liquid (c") - if present - is removed from said wet film on said surface of said solid substrate by exposing said wet film to a temperature in the range of from 20 °C to 120 °C, preferably 40 °C to 120 °C, most preferably 80 °C to 120 °C.
  • the composition for preparing the separator layer does not contain a carrier liquid (c"), and the wet film formed by applying the composition for preparing the separator layer to said surface of said composite layer has a thickness in a range of from 0.05 ⁇ to 1500 ⁇ , preferably of from 0.05 ⁇ to 1000 ⁇ . Said thickness is also referred to as "wet thickness”.
  • Said counter electrode layer comprises an electroactive material capable of repeatedly inserting and releasing ions to compensate for changes of the oxidation state of the metal of the electrochromic oxide in the nanoobjects (a) present in the electrochromic composite layer.
  • the electrochromic composite layer and the counter electrode layer are connected to a direct voltage source. Between the electrochromic composite layer and the counter electrode, virtually no electrons are transferred across the separator layer.
  • Said counter electrode layer may comprise an electroactive material which independent from its state of oxidation is substantially optically transparent or has an electrochromic effect involving a color change significantly less pronounced than that of the electrochromic metal oxide in the nanoobjects (a) of the electrochromic composite layer.
  • Suitable electro- active materials include, but are not limited to tin oxide, cerium oxide, and transparent polymers capable of intercalating lithium ions.
  • said counter electrode layer comprises an electroactive material which exhibits an electrochromic effect having a dependence on the applied electrochemical potential which is opposite to the electrochromic effect of tungsten oxide.
  • the counter electrode layer is obtained by depositing an electroactive material on the surface of said second solid substrate.
  • Depositing the electroactive material e.g. an electrochromic material
  • said counter electrode layer comprises one or more oxides of nickel.
  • At least one of the composition according to the first aspect of the present invention (which is used for preparing the composite layer) and the composition for preparing the separator layer must contain an electrolyte (h), (h"), resp.
  • said counter electrode layer is a second composite layer comprising
  • (a') nanoobjects comprising one or more electrochromic compounds selected from the group consisting of oxides of elements selected from the group consisting of transition metals, rare earth elements, and elements of groups 12, 13 and 14 with the exception of carbon and tungsten
  • said second composite layer further comprises
  • elements of groups 12, 13 and 14 refer to elements of groups 12, 13 and 14 of the periodic table of the elements according to lUPAC notation.
  • said electroconductive nanoobjects (i') are nanowires comprising, preferably consisting of, materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel.
  • said article comprises a first composite layer arranged on a surface of said first solid substrate, and a second composite layer arranged on a surface of said second solid substrate.
  • Said article comprises a multilayer structure which in the direction of stack- ing consists of a first solid substrate, a first composite layer as defined above, a separator layer, a second composite layer as defined above and a second solid substrate.
  • said separator layer has a first surface and a second surface opposite to said first surface, wherein said first surface of said separator layer is in contact with a surface of said first composite layer facing away from said first solid substrate, and said second surface of said separator layer is in contact with a surface of said second composite layer facing away from said second solid substrate.
  • the nanoobjects (a') comprise electrochromic compounds which are different from the electrochromic oxides of tungsten comprised by the nanoobjects (a) of the first composite layer.
  • the nanoobjects (a) of the first composite layer comprise one or more oxides of tungsten
  • the nanoobjects (a') of the second composite layer comprise one or more oxides of nickel.
  • the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g') having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer, and - if present - the electrolyte (h') is the same as the electrolyte (h) in the first composite layer.
  • aprotic organic liquid (g') having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer
  • - if present - the electrolyte (h') is the same as the electrolyte (h) in the first composite layer.
  • a first layer assembly comprising a first solid substrate having a surface and arranged on said surface of said first solid substrate a first composite layer as defined above, and optionally a separator layer disposed on a surface of said first composite layer facing away from said first solid substrate or a wet film obtained by applying the above-described composition for forming a separator layer on said surface of the first composite layer facing away from said first solid substrate, and
  • a second layer assembly comprising a second solid substrate having a surface and arranged on said surface of said second solid substrate a second composite layer as defined above, and optionally a separator layer disposed on a surface of said second composite layer facing away from said second solid substrate or a wet film obtained by applying the above-defined composition for forming a separator layer on said surface of the second composite layer facing away from said second solid substrate,
  • At least one of said first and second layer assembly comprises a separator layer or a wet film as defined above
  • Bonding may be achieved by polymerizing the monomers (d") in said wet film obtained by applying the above-defined composition for preparing a separator layer on the surface of the first resp. second composite layer as defined above, or by completing the polymerization of the polymerizable moieties (d), (d'), (d"), resp. in said layers to be bonded.
  • said counter electrode layer is a second composite layer as defined above and said separator layer comprises
  • (h) optionally at least one electrolyte having cations selected from the group consisting of H + , Li + , Na + and K + dissolved in said aprotic organic liquid (g").
  • Disposing a separator layer on the surface of said first composite layer facing away from said first solid substrate and/or on the surface of said second composite layer facing away from said second solid substrate comprises the steps as described above.
  • the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g') resp. (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer, and - if present - the electrolyte (h') resp. (h") is the same as the electrolyte (h) in the first composite layer.
  • the polymerizable moieties (d') resp. (d") are the same as the polymerizable moieties (d) in the composition for preparing the first composite layer
  • the aprotic organic liquid (g') resp. (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the composition for preparing the first composite layer
  • - if present - the electrolyte (h') resp. (h") is the same as the electrolyte (h) in the composition for preparing the first composite layer.
  • an electrochromic device comprising a first composite layer as defined above and one or both of a separator layer as defined above and a second composite layer as defined above, at least one of said layers must contain an electrolyte (h), (h'), (h"), resp. It has been found that ions from the electrolyte which is present in one of said layers may enter the other layer(s) by diffusion and migration, thereby providing for sufficient ionic conductivity across the respective layers.
  • At least one of the composition according to the first aspect of the present invention (which is used for preparing the first composite layer), the composition for preparing the separator layer and the composition for preparing the second composite layer must contain an electrolyte (h), (h'), (h"), resp.
  • Water may also provide for ionic conductivity of the composite layers and the separator layer, as explained above. However, in the context of this disclosure, water is not an electrolyte (h), (h'), (h") as defined above.
  • a specifically preferred article for production of or use in an electrochromic device com- prises
  • a first composite layer arranged on said surface of said first solid substrate, a first composite layer a second solid substrate having a surface
  • said first composite layer comprises
  • (h) optionally at least one electrolyte having cations selected from the group consisting of H + , Li + , Na + and K + dissolved in said aprotic organic liquid (g) and
  • said second composite layer comprises
  • a matrix formed of one or more organic polymers and dispersed within said matrix (a') nanoobjects comprising one or more electrochromic oxides of nickel (g') an aprotic organic liquid having a boiling point of 120 °C or higher, (h') optionally at least one electrolyte having cations selected from the group consisting of H + , Li + , Na + and K + dissolved in said aprotic organic liquid (g').
  • said first composite layer comprises
  • an aprotic organic liquid selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
  • (h) optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g)
  • salts selected from the group consisting of scandium bis(trifluoromethane)sulfonimide, yttrium bis(trifluoromethane)sulfonimide, aluminum bis(trifluoromethane)sulfonimide, lanthanum bis(trifluoro- methane)sulfonimide, cerium bis(trifluoromethane)sulfonimide, nickel bis(fluorosulfonyl)imide, copper bis(fluorosulfonyl)imide, zinc bis(fluorosul- fonyl)imide, yttrium trifluoromethylsulfonate, aluminum trifluoromethylsulfonate, lanthanum trifluoromethylsulfonate, cerium trifluoromethylsulfonate, and yttrium fluorosulfonate
  • an aprotic organic liquid selected from the group consisting of ethanol, methanol,
  • (h') optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g").
  • electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g").
  • the second composite layer of the above-defined specifically preferred article is obtainable using the composition or according to the process described in a patent application filed by the same applicant on the same day as the present application.
  • an article for production of or use in an electrochromic device further comprises a support layer attached to the surface of the first solid substrate facing away from the composite layer and/or a support layer attached to the surface of the second solid substrate facing away from said counter electrode layer.
  • a first support layer is attached to the surface of the first solid substrate facing away from the composite layer and a second support layer is attached to the surface of the second solid substrate facing away from said counter electrode layer.
  • the first and second solid substrate comprise materials from the group of organic polymers and are in the form of foils, films, webs, and the first and second support layer comprise glass.
  • a third support layer may be attached to the surface of the first support layer facing away from the first solid substrate and/or a fourth support layer may be attached to the surface of the second support layer facing away from the second solid substrate.
  • a third support layer is attached to the surface of the first support layer facing away from the first solid substrate and a fourth support layer is attached to the surface of the second support layer facing away from the second solid substrate.
  • the first, second, third and fourth support layer comprise glass.
  • Said support layers comprise one or more materials selected from the group consisting of glasses, metals and organic polymers.
  • Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass.
  • the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing outwardly.
  • Attaching said first resp. second support layer to said first resp. second solid substrate preferably comprises applying an adhesive between the support layer and the surface of the solid substrate to which said support layer has to be attached.
  • Attaching said third resp. fourth support layer to said first resp. second support layer preferably comprises applying an adhesive.
  • Suitable adhesives are thermoplastics, e.g.
  • polyvinylbutyral polyvinylalcohol
  • polyvinylacetate polyvinylacetate
  • ethylene-vinylacetate-copolymers polyurethanes
  • ionomer resins commercially available e.g. under the trade name SentryGlas®
  • PMMA polymethylmethacrylate
  • the present invention further relates to the use of an article as defined above resp., an electrochromic device as defined above in buildings, furniture, cars, trains, planes and ships as well as to the in facades, skylights, glass roofs, stair treads, glass bridges, canopies, railings, car glazing, train glazing.
  • the present invention further relates to insulating glass units, windows, rotating windows, turn windows, tilt windows, top-hung windows, swinging windows, box windows, horizontal sliding windows, vertical sliding windows, quarterlights, store windows, skylights, light domes, doors, horizontal sliding doors in double-skin facades, closed cavity facades, all- glass constructions, D3-facades (Dual, Dynamic Durable Facade), facade glass construction elements (e.g. but not limited to fins, louvres), interactive facades (facades reacting on an external impulse e.g.
  • a motion control but not limited to a motion control, a radio sensor, other sensors
  • curved glazing formed glazing, 3D three-dimensional glazing, wood-glass combinations, over head glazing, roof glazing, bus stops, shower wall, indoor walls, indoor separating elements in open space offices and rooms, outdoor walls, stair treads, glass bridges, canopies, railings, aquaria, balconies, privacy glass and figured glass.
  • the present invention further relates to thermal insulation, i.e. insulation against heat, in- sulation against cold, sound insulation, shading and/or sight protection.
  • the present invention is preferably useful when combined with further glass layers to an insulation glass unit (IGU), which can be used for building facades.
  • IGU might have a double (Pane 1 + Pane 2), or triple glazing (Pane 1 + Pane 2 + Pane 3), or more panes.
  • the panes might have different thicknesses and different sizes.
  • the panes might be of tempered glass, tem- pered safety glass, laminated glass, laminated tempered glass, safety glass.
  • the device according to the present application may be used in any of the panes 1 , 2, 3. Materials can be put into the space between the panes.
  • such materials might be argon, xenon, nitrogen, wooden objects, metal objects, expanded metal, prismatic objects, blinds, louvres, light guiding objects, light guiding films, light guiding blinds, 3-D light guiding objects, sun protecting blinds, movable blinds, roller blinds, roller blinds from films, translucent materials, capillary objects, honey comb objects, micro blinds, micro lamella, micro shade, micro mirrors insulation materials, aerogel, integrated vacuum insulation panels, holographic elements, integrated photovoltaics or combinations thereof.
  • the present invention further relates to the use in heat-mirror glazing, vacuum glazing, multiple glazing and laminated safety glass.
  • the present invention further relates to the use in transportation units, preferably in boats, in vessels, in spacecrafts, in aircrafts, in helicopters, in trains, in automotive, in trucks, in cars e.g. but not limited to windows, separating walls, light surfaces and background lighting, signage, pass protection, as sunroof.
  • the present invention is preferentially useful when combined with further glass layers to an insulation glass unit (IGU), which can be used for building facades.
  • IGU insulation glass unit
  • compositions were obtained in an analogous manner as in the examples in WO 2016/128133.
  • the nanoparticles were either commercially available. All other constituents were all commercially available.
  • compositions were evaluated as follows: A composition was considered instable if there was a phase separation after two hours such that there was a clear supernatant of 30 % or more in height regarding to the total filling height.
  • composition according to the first aspect of the present invention comprising
  • compositions 1 to 15 comprising the above-defined constituents (a), (c), (d), (e) and (g) and a commercially available dispersing agent (for details, see table 1 ) instead of water were prepared.
  • concentration of constituents (a), (d), (e) and (g) was the same as in the composition according to the invention.
  • the dispersing agents used for the comparison compositions were found to be able to prevent agglomeration and settling of dispersed nanoparticles (a) as defined above in a composition comprising a carrier liquid selected from ethanol and 2-propanol and none of above-defined components (d), (e) and (g) at least for a couple of hours.
  • a composition comprising a carrier liquid selected from ethanol and 2-propanol and none of above-defined components (d), (e) and (g) at least for a couple of hours.
  • the specific composition of the commercially available dispersing agents was not disclosed by the suppliers. For this reason, in table 1 certain dispersing agents are identified by their trade names.
  • the agglomeration behavior of the composition according to the invention and the comparison compositions was monitored as described above. Only few of the comparison compositions met the above-defined condition of stability.
  • composition according to the invention and comparison compositions 10-15 which exhibited no significant agglomeration and settling over two hours were used as inks for preparing composite layers as defined above.
  • the substrate was in each case a glass plate having a surface coating of indium-tin-oxide (ITO).
  • ITO indium-tin-oxide
  • a wet film was formed in each case by spin-coating the ink on said ITO-coated surface.
  • the monomers (d) were copolymerized.
  • the copolymerization was initiated by means of UV irradiation. Thereafter, the coated substrates were heated on a hot plate.
  • the electrochromic behavior of the composite layers obtained as described above was studied by means of cyclic voltammetry acting as working electrode in the potential range -1.5 V to +1.5 V in a three electrode cell using a 0.5 molar solution of lithium trifluorome- thylsulfonate in 1 ,2-propylene carbonate as the electrolyte, platinum as the counter elec- trade and Ag/Ag + as the reference electrode.
  • Only the composite layer obtained from the composition according to the invention exhibited reversible electrochromic behavior. It adopted a blue color when the potential was scanned in the cathodic direction and discolored when the potential was scanned back in the anodic direction.
  • compositions according to the invention comprising the above-defined constituents (a), (b), (c), (d), (e), (g) and an electrolyte (h) (see table 2, concentration in the above-defined preferred range) was monitored. In each case either no visible change or only a slight colloidal turbidity was observed.
  • Table 2 concentration in the above-defined preferred range
  • Lithium hexafluorophosphate slight colloidal turbidity
  • Lithium chloride slight colloidal turbidity
  • Lithium bromide slight colloidal turbidity Lithium difluorophosphate no visible change
  • composition according to the invention agglomeration and settling of the dispersed nanoparticles (a) is effectively suppressed, although said composition comprises constituents (d), (e), (g) and optionally (h) which may have a detrimental influ- ence on the stability of the dispersed nanoparticles (a), as shown in the comparison tests described above.
  • a composition according to the invention can be used as an ink for preparing a composite layer which exhibits a reversible electrochromic effect.

Abstract

Described are compositions comprising dispersed nanoobjects comprising one or more oxides of tungsten and processes for preparing a layer comprising such nanoobjects on a surface of a solid substrate.

Description

Compositions comprising dispersed nanoparticles of electrochromic oxide
The present invention relates to compositions (also referred to as inks) comprising nanoobjects and to a process for preparing a layer comprising nanoobjects on a surface of a solid substrate.
Electronic devices e.g. optoelectronic devices or electrochromic devices often contain functional layers comprising nanoobjects, e.g. nanoobjects comprising an electrochromic material. Such functional layers are commonly prepared by wet processing techniques wherein a liquid composition (commonly referred to as an "ink") comprising suspended nanoobjects is applied to a surface of a solid substrate. Compositions comprising suspended nanoobjects are also used for preparing any other objects and formulations comprising nanoobjects.
It is commonly known that nanoobjects, when dispersed in a liquid phase are prone to agglomeration and/or settling. A variety of proposals for solving this problem is disclosed in the prior art. For instance, WO 2016/128133 A1 proposes addition of dispersing agents in the form of metal salts to inks comprising nanoobjects. Preferred salts are formiates, acetates, citrates, oxalates, nitrates and halogenides of metal cations from the group consisting of Zn, Al, Y, Pb, Bi Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Mg, Ca, Sr and Ba. Related art is also
CN 106 497 252 A
EP 2 631 008 A1.
There is an ongoing demand for compositions comprising dispersed nanoobjects wherein agglomeration and/or settling of said nanoobjects is effectively suppressed over a long duration, even in case of a high concentration and/or small size of said dispersed nanoobjects.
According to a first aspect of the present invention, there is provided a composition comprising
(a) nanoobjects comprising one or more oxides of tungsten
(b) water
(c) an organic liquid having a boiling point below 120 °C
(d) one or more kinds of polymerizable moieties
(e) optionally one or more initiators for initiating radical polymerization of said one or more kinds of polymerizable moieties
(f) optionally one or more organic polymers suspended or dissolved in the liquid external phase of the composition
(g) an aprotic organic liquid having a boiling point of 120 °C or higher
(h) at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+,
(i) optionally electronically conductive nanoobjects not comprising any oxides of tungsten.
A composition according to the present invention is in the form of a suspension, also referred to as slurry. In the context of certain technical application fields, such composition is also referred to as an ink. Preparation of suspensions is known in the art. The term "suspension" denotes a dispersion comprising a continuous phase (in the literature sometimes referred to as an external phase e.p.) that is liquid and at least one dispersed phase (in the literature sometimes referred to as an internal phase i.p.) that is solid and does not dissolve in said continuous phase which is liquid. In a suspension which forms a composition according to the present invention, the nanoobjects (a) form a dispersed phase, which is dispersed within the liquid external phase. The external liquid phase consists of the above- defined liquid constituents (b), (c) and (g) and any constituents which are dissolved in said liquids.
Surprisingly it has been found that in a composition comprising dispersed nanoobjects (a) comprising one or more oxides of tungsten as defined above, the combination of water and an organic liquid having a boiling point below 120 °C is capable of effectively suppressing agglomeration and/or settling of said dispersed nanoobjects (a) over a long duration, even in case of high concentrations of said nanoobjects (a), without detrimentally affecting other properties of said nanoobjects and without detrimental effects towards other constituents of said composition. Thus, addition of dispersing agents as known in the prior art, e.g. the metal salts disclosed in WO 2016/128133 A1 , is not necessary. This is a significant advantage, since when an electrochromic layer is prepared using an ink containing such dispersing agents, said dispersing agents remain in said layer and may have a detrimental influence on the properties of said electrochromic layer.
The constituents of the composition according to the invention are now described in detail. Said nanoobjects (a) comprise one or more electrochromic oxides of tungsten. Preferably, said nanoobjects (a) consist of one or more oxides of tungsten.
According to ISO/TS 27687:2008 (as published in 2008), the term "nanoobject" refers to an object having one, two or three external dimensions in the nanoscale, i.e. in the size range from approximately 1 nm to 100 nm. According to ISO/TS 27687:2008, nanoobjects having one external dimension in the nanoscale, while the other two external dimensions are significantly larger, are generally referred to as nanoplates. Said one external dimension in the nanoscale corresponds to the thickness of the nanoplate. The two significantly larger dimensions differ from the nanoscale dimension by more than three times. The two larger external dimensions are not necessarily in the nanoscale. Another common term for denoting a nanoobject having one external dimension in the nanoscale, while the other two external dimensions are significantly larger, is "nanoflake".
According to ISO/TS 27687:2008, nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension is significantly larger, are generally re- ferred to as nanofibers. The third significantly larger dimension differs from the nanoscale dimensions by more than three times. The largest external dimension is not necessarily in the nanoscale. Said largest external dimension corresponds to the length of the nanofibers. Nanofibers typically have a cross section close to circular shape. Said cross section extends perpendicularly to the length. Said two external dimensions which are in the nanoscale are defined by the diameter of said circular cross section. Electrically conductive nanofibers are also referred to as nanowires. Hollow nanofibers (irrespective of their electrical conductivity) are also referred to as nanotubes. Nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension (length) is significantly larger, which are rigid (i.e. not flexible) are commonly referred to as nanorods. Nanoobjects having two similar external dimensions in the nanoscale, while the third external dimension (length) is significantly larger, and have a cross section close to rectangular shape extending perpendicularly to the length, are commonly referred to as nanoribbons.
According to ISO TS 27687:2008, nanoobjects having all three external dimensions in the nanoscale, wherein the length of the longest axis and the length of the shortest axis of the nanoobject differ not significantly, are generally referred to as nanoparticles. The length of the longest axis and the length of the shortest axis differ by not more than three times.
Approximately isometric nanoparticles, i.e. the aspect ratio (longest : shortest direction) of all three orthogonal external dimensions is close to 1 , are commonly referred to as nano- spheres. Preferably, the nanoobjects of constituent (a) of the present invention are nanoparticles. Preferred nanoparticles are approximately isometric, i.e. the aspect ratio (longest : shortest direction) of all 3 orthogonal external dimensions is in the range of from 1 to 2. Especially preferred nanoparticles are nanospheres.
Particularly preferred nanoparticles are primary particles having a primary particle diameter of 1 nm to 100 nm, preferably 3 nm to 50 nm (measured by nitrogen absorption, X-ray diffraction or transmission electron microscopy). Preferred are nanoparticles having a primary particle diameter of less than 20 nm, more preferably less than 15 nm, further preferably 12 nm or less. According to DIN 53206-1 : 1972-08, the term "primary particles" refers to entities which are discernible as individuals by means of optical microscopy or transmis- sion electron microscopy. Advantageously, the nanoobjects are nanoparticles which in suspension have a hydrody- namic size D90 of less than 100 nm (measured by dynamic light scattering or centrifugal sedimentation techniques).
Electrochromic materials are characterized by an ability to change their optical properties, reversibly, and persistently, when a voltage is applied across them (see Claes G. Granqvist, Solar Energy Materials & Solar Cells 99 (2012) 1-13). This ability is herein also referred to as the "electrochromic effect". A change of the optical absorption of the electrochromic material occurs when electrons are transferred to or away from the electrochromic material, along with charge balancing ions entering from an adjacent electrolyte. Certain electro- chromic materials have the property of exhibiting a change, evocation, or bleaching of color (in the visible range of the electromagnetic spectrum) as effected either by an electron- transfer (redox) process or by a sufficient electrochemical potential (see Mortimer, R. J.: "Electrochromic materials", Annu. Rev. Mater. Res. 201 1 . 41 :241-68). However, as used herein, the term "electrochromic material" is not limited to materials exhibiting a change, evocation, or bleaching of color (in the visible range of the electromagnetic spectrum). Thus, materials changing their optical absorption, e.g. in the UV or IR range of the electromagnetic spectrum without a visible color change, are herein also referred to as "electrochromic".
Electrochromic metal oxides are known in the art, see e.g. Mortimer, R. J.: "Electrochromic materials", Annu. Rev. Mater. Res. 201 1 . 41 :241-68 and Granqvist, C. G.: "Oxide electro- chromics: An introduction to devices and materials", Solar Energy Materials & Solar Cells 99 (2012) 1-13.
Oxides of tungsten are known to have an electrochromic effect. Tungsten oxide WO3 which is virtually colorless colors blue during cathodic reduction in combination with simultaneous intercalation of charge-balancing cations M (typically one of H+, Li+, Na+, K+) thus forming MxW03. The blue color vanishes during anodic oxidation.
Preparation of nanoobjects (a) comprising one or more electrochromic oxides of tungsten is known in the art. For instance, said nanoobjects (a) are nanoparticles synthesized by a gas phase pyrolysis process, preferably flame spray synthesis. Such nanoparticles are commercially available. Constituent (b) of the composition according to the invention is water.
Constituent (c) of the composition according to the invention is an organic liquid having a boiling point of less than 120 °C. The boiling point refers to the standard pressure of 101 .325 kPa. Constituents (b) and (c) form a carrier liquid having a boiling point below 120 °C. Said carrier liquid is merely a vehicle for wet processing and usually does not remain in the layer to be formed from the above-defined composition.
Preferably said organic liquid having a boiling point below 120 °C (c) has a polarity index > 4 according to the polarity scale, based on the polarity index of water being 9 (V.J. Barwick, Trends in Analytical Chemistry, vol. 16, no. 6, 1997, p.293ff, Table 5).
Said organic liquid having a boiling point below 120 °C is not polymerizable.
Preferably said organic liquid having a boiling point below 120 °C is selected from the group consisting of alcohols, amines, carbonic acids, esters, ketones, organic carbonates, poly- ethers, sulfides and nitriles and mixtures thereof. More preferably, said organic liquid hav- ing a boiling point below 120 °C is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert.-butanol, 2-butanone, 2-pen- tanone, methyl isobutyl ketone, dimethyl carbonate, ethyl methyl carbonate, 1 ,2-dimethoxy- ethane, acetonitrile, pyridine, propionitrile, dimethylamine, formic acid, acetic acid, ethyl acetate, dimethoxyethane, acetone, dimethyl carbonate, dioxane, trifluoromethyl methyl carbonate, ethyl methyl carbonate, 2-methyltetrahydrofuran, chloroform and mixtures thereof. Especially preferred ones are selected from the group consisting of ethanol, methanol, 2-propanol, 2-methyl tetrahydrofuran and mixtures thereof.
A composition according to the invention may be used as an ink for preparing an electro- chromic layer. For further details, see below. A composition according to the invention further comprises
(d) one or more kinds of polymerizable moieties.
The term "polymerizable moieties" as used herein includes polymerizable monomers and polymerizable oligomers. Said polymerizable moieties (d) are dissolved in the liquid phase of the composition.
Said polymerizable moieties (d) are precursors of a polymer matrix. In the process of preparing a layer from the above-defined composition, said polymerizable moieties form a polymer matrix by polymerization on a surface of a solid substrate to which the above- defined composition has been applied. In a layer obtained from an above-defined preferred composition according to the present invention, said matrix binds and accommodates the nanoobjects (a) and optionally further constituents (see below) within said layer, fills the voids between said nanoobjects (a), provides mechanical integrity and stability to the layer and binds the layer to the surface of the solid substrate.
Preferably said polymerizable moieties are selected from the group consisting of alkyl acrylates, alkyl methacrylates, hydroxyalkyi acrylates, hydroxyalkyi methacrylates, vinyl chloride, vinyl fluoride, acrylonitrile, vinylidene fluoride, vinylidene chloride, hexafluoropropyl- ene, trifluoroethylene, tetrafluoroethylene, tetrahydrofurane, vinylpyrrolidone, polyisocya- nates in combination with polyols and/or diamines.
Most preferably, said polymerizable moieties are co-polymerizable monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and from the group consisting of hydroxyalkyi acrylates and hydroxyalkyi methacrylates. Herein preferably the molar ratio between the total amount of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and the total amount of monomers selected from the group of hydroxyalkyi acrylates and hydroxyalkyi methacrylates is in the range of from 0.0002 to 50000, preferably 0.4 to 200. Preferably said polymerizable monomers are butyl acrylate and hydroxybutyl acrylate.
In cases where the polymerizable moieties (d) are polymerizable by radical polymerization, said composition preferably further comprises
(e) one or more initiators for initiating radical polymerization of said one or more kinds of polymerizable moieties.
Suitable initiators are known in the art and commercially available. Preferably, said initiators are selected from the group consisting of compounds which decompose into radicals when exposed to electromagnetic irradiation. Optionally, a composition according to the invention further comprises
(f) one or more organic polymers suspended or dissolved in the liquid external phase of the composition.
In the process of preparing a layer from the composition said polymers are incorporated in the above-defined matrix.
The polymers (f) are either dissolved in the liquid external phase of the composition, or -in case they are not soluble in said liquid phase- they are present in the form of particles which are suspended within said liquid phase.
Preferably said polymers (f) are selected from the group consisting of polyalkyl acrylates, polyalkyl methacrylates, polyhydroxyalkyl acrylates, polyhydroxyalkyl methacrylates, polyvinyl chloride, polyvinyl fluoride, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polyhexafluoropropylene, polytrifluorethylene, polytetrafluoroethylene, polytetra- hydrofuran, polyvinylpyrrolidone, polyurethanes, polyethylene oxides.
A composition according to the invention further comprises
(g) an aprotic organic liquid having a boiling point of 120 °C or higher.
The boiling point refers to the standard pressure of 101.325 kPa.
In the composition according to the present invention, said aprotic organic liquid (g) is mixed with the carrier liquid so that a common liquid phase exists in the above-defined composition. Accordingly, the organic liquid (c) having a boiling point below 120 °C and the aprotic organic liquid (g) having a boiling point of 120 °C or higher are selected to be mis- cible with water (constituent (b)).
Said aprotic organic liquid is selected to have a boiling point of 120 °C or higher, in order to allow said aprotic organic liquid (g) to remain in a layer prepared from the above-defined composition, when heat is applied during the steps of removing the carrier liquid and poly- merizing the polymerizable moieties.
Said aprotic organic liquid (g) is not polymerizable.
Said aprotic organic liquid (g) is selected to be capable of allowing for dissolution and dissociation of at least one electrolyte (h) as defined below. Preferably said aprotic organic liquid (g) is selected from the group consisting of organic carbonates, alcoholes, amides, carboxylic acid esters, ethers, polyethers, ketones, lactones, lactames, phosphoric acid esters, sulfones, sulfoxides, sulfonates, urea, thiourea, derivatives of urea resp. thiourea, and mixtures thereof. Derivatives of urea resp. thiourea are compounds wherein one or more of the hydrogen atoms of urea resp. thiourea are substituted. Examples are ethylene urea (2-lmidazolidon) Ν,Ν'-dimethylpropylene urea, N- (2-hydroxyethyl)ethylene urea and the corresponding thiourea derivatives.
Most preferably, said aprotic organic liquid (g) is selected from the group consisting of ethylene carbonate, 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, 1 ,2-butylene carbonate, 1 ,3-butylene carbonate, 1 ,4-butylene carbonate, 2,3-butylene carbonate, ethylene glycol, diethylene glycol, diethyl carbonate, gamma-butyrolactone, gamma-valerolactone, sulfolane, dimethyl sulfoxide, 1 ,3-deimethyl-3,4,5,6-tetrahydro-2(1 H)-pyrimidinone (DMPU) and mixtures thereof.
Especially preferred are ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3- propylene carbonate and mixtures thereof.
Optionally, a composition according to the invention further comprises
(h) at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+. The term "electrolyte" is known in the art and denotes a substance which is capable of dissociating into mobile ions. In a layer prepared from the above-defined composition, said electrolyte (h) dissolved in said aprotic organic liquid (g) provides ionic conductivity.
Preferably, said composition does not comprise any salts which are not selected from the group of electrolytes comprising at least one cation from the group consisting of H+, Li+, Na+ and K+
In the context of this disclosure, water does not belong to the electrolytes (h) as defined above. Accordingly, said electrolyte comprises at least one anion which is different from OH" or at least one cation from the group consisting of Li+, Na+ and K+.
Preferred electrolytes (h) are lithium salts. Preferably, said electrolytes (h) are selected from the group consisting of lithium aluminum chloride (LiAICU); lithium hexafluorosilicate (Li2SiFe); lithium hexafluoroantimonate (LiSbFe); LiX(RS02)n wherein n=1 and X=0 or S, n=2 and X=N or P, n=3 and X=C or Si, and R in each case is CmH2m+i-nFn wherein m = 0-20, n = 0-21 ; lithium fluoride (LiF); lithium nitrate (UNO3); lithium perchlorate (LiCIC ); lithium tetrafluoroborate (L1BF4); lithium tetrakis(pentafluorophenyl)borate; lithium difluorophosphate (L1PO2F2); lithium hexafluoro- phosphate (LiPFe); lithium hexafluoroarsenate (LiAsFe); lithium bis(fluorosulfonyl)imide (LiN(S02F)2); lithium trifluoromethylsulfonate (UCF3SO3); LiN(S02CnF2n+i)2 wherein n = 2 to 20; LiC[(CnF2n-i)S02]3 wherein n = 2 to 20; Li(CnF2n+i)S02 wherein n = 2 to 20; lithium bis(trifluoromethane)sulfonimide (LiN(CF3S02)2, also referred to as lithium bis-trifluorome- thylsulfonylimide); lithium tris-trifluoromethyl sulfonylmethide (LiC(CF3S02)3); lithium bisox- alatoborate (LiB(C204)2); lithium difluoro(oxalate)borate (LiBF2(C204)); lithium difluoro(bi- soxalato)phosphate and lithium tetrafluoro(oxalate)phosphate. Especially preferred are lithium bis(fluorosulfonyl)imide (LiN(S02F)2), and lithium bis(trifluoromethane)lsulfonimide
Figure imgf000011_0001
Most preferably, said at least one electrolyte (h) is selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide.
Optionally, a composition according to the invention further comprises
(i) electronically conductive nanoobjects not comprising any oxide of tungsten.
Said electronically conductive nanoobjects (i) form a dispersed phase, which is dispersed within the liquid external phase of the composition according to the present invention.
In a layer prepared from the above-defined composition, said electronically conductive nanoobjects deposited on a surface of a solid substrate may form a conductive network of adjacent and overlapping electronically conductive nanoobjects capable of carrying an electric current.
Preferably said electroconductive nanoobjects (i) have two external dimensions in the range of from 1 nm to 100 nm, and their third external dimension is in the range of from 1 μιη to 100 μιτι, in each case determined by transmission electron microscopy. Typically, said two external dimensions which are in the range of from 1 nm to 100 nm are similar i.e. they differ in size by less than three times. The third dimension of said electroconductive nanoobjects is significantly larger, i.e. it differs from the other two external dimensions by more than three times. Preferably, said electroconductive nanoobjects (i) are nanowires as defined in ISO TS 27687:2008 (as published in 2008) (for details, see above).
Preferably, the electronically conductive nanoobjects (i) are nanowires having a length in the range of from 1 μητι to 100 μιτι, preferably of from 3 μιτι to 50 μιτι, more preferably of from 10 μιτι to 50 μιτι, and a diameter in the range of from 1 nm to 100 nm, preferably of from 2 nm to 50 nm, more preferably of from 15 nm to 30 nm, length and diameter in each case being determined by transmission electron microscopy.
Preferably, said electronically conductive nanoobjects are nanowires comprising materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel. More preferably, said electronically conductive nanoobjects are nanowires consisting of materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel. Compositions according to the invention which comprise the above-defined constituents (h) and (i) are preferably obtained by a method following the teaching of non-prepublished patent application having the application number PCT/EP2017/055320. Basically said method comprises providing a first suspension comprising above-defined constituents (a), and at least one of (b) and (c), providing a second suspension comprising above-defined constituents (i), and at least one of (b) and (c) (with the proviso that at least one of the first and the second suspension contains constituent (b) and at least one of the first and the second suspension contains constituent (c), adding together said first suspension and said second suspension to obtain a third suspension comprising above-defined constituents (a), (b), (c), and (i), and admixing to said third suspension the above-defined constituents (d), (g), (h) and optionally (e) and (f).
A composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d) and (g) and optionally one, more or all of the above-defined constituents (e), (f), (h) and (i) contains a single continuous liquid phase comprising the constituents (b), (c) and (g) which at standard pressure 101.325 kPa are liquid at temperatures below 120 °C and constituent (d) and - if present - constituent (e) and constituent (f) (if present in the form of soluble polymers) which are dissolved in said liquid phase. Constituents (a) and - if present - constituent (i) and constituent (f) (if present in the form of polymer particles) each form a dispersed phase, which is dispersed within the liquid external phase. A composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d), (g) and (h) and optionally one, more or all of the above-defined constituents (e), (f), and (i) may be used for preparing an electrochromic composite layer which in an electrochromic device can function as an electrochromic electrode. An electrochromic composite layer obtainable from a composition which contains the above-defined constituents (a), (b), (c), (d), (g), (h) and optionally one, more or all of the above-defined constituents (e), (f) and (i), comprises
a matrix formed of one or more organic polymers
and dispersed within said matrix
(a) nanoobjects comprising one or more electrochromic oxides of tungsten
(g) an aprotic organic liquid having a boiling point of 120 °C or higher,
(h) at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g).
Optionally, an electrochromic composite layer as defined above further comprises (i) electronically conductive nanoobjects not comprising any oxides of tungsten dispersed within said matrix formed of one or more organic polymers.
The term electrochromic composite layer denotes a layer comprising discrete nanoobjects (a) comprising one or more electrochromic oxides of tungsten as defined above and constituents (g), (h) and optionally (i) dispersed within a continuous phase (matrix) extending throughout said layer. Both, an electronically conductive network and an ionically conductive network extend throughout the electrochromic composite layer providing for the transport of electrons and ions to and away from the dispersed nanoobjects comprising electrochromic compounds as defined above. Further constituents may be dispersed in the matrix, each fulfilling a specific function and interacting with the other constituents. Within the electrochromic composite layer, the matrix provides mechanical integrity and stability and binds and accommodates the above-defined constituents of the electrochromic composite layer which are dispersed within said matrix. Without being bound to theory, it is believed that the nanoobjects (a) comprising one or more electrochromic oxides of tungsten as defined above and -if present - the electronically conductive nanoobjects (i) as defined above, which are dispersed within the matrix, form a network extending throughout the electrochromic composite layer providing for the transport of electrons towards and away from the nanoobjects (a). Without being bound to theory, it is believed that in the electrochromic composite layer of the electrochromic device according to the present invention said aprotic organic liquid (g) including said dissolved electrolyte (h) as defined above is confined within pores extending through the matrix, thus providing a network for the transport of ions to and away from the nanoobjects (a).
Water may also provide for ionic conductivity of the electrochromic composite layer. The amount of water that remains in said system consisting of water (b) and two other liquids (c) and (g) as defined above can be estimated according to Raoult's law or can be determined from experimental data, as known by the skilled person. However, in the context of this disclosure, water is not an electrolyte (h) as defined above.
A composition according to the present invention which contains the above-defined constituents (a), (b), (c), (d) and (g) and optionally one, more or all of the above-defined constituents (e), (f), and (i) may be used for preparing a precursor layer of an electrochromic composite layer. A precursor layer of an electrochromic composite layer differs from an electrochromic composite layer as defined above in that said precursor layer does not contain any electrolytes (h). A precursor layer of an electrochromic composite layer may be transferred into an electrochromic composite layer by allowing migration or diffusion of ions of an electrolyte (h) as defined above from another source (see below) into said precursor layer.
Where appropriate, an electrochromic composite layer as defined above and a precursor layer thereof as defined above are herein commonly denoted as "a composite layer".
Thus, a composition according to the invention which may be used for preparing an electrochromic composite layer or a precursor layer thereof comprises
precursors (in the form of polymerizable moieties and optionally dissolved or suspended polymers) of the organic polymer matrix of the composite layer, and the above-defined constituents of the composite layer which are to be dispersed within said organic polymer matrix, and
a carrier liquid having a boiling point of less than 120 °C which does not become a constituent of the composite layer but merely acts as a vehicle for wet-processing. Preferably, in a composition according to the present invention
(a) the amount of nanoobjects comprising one or more electrochromic oxides of tungsten above is in the range of from 0.1 wt.-% to 20 wt.-%, preferably 0.5 wt.-% to 10 wt.-%,
(b) the amount of water is in the range of from 0.04 wt.-% to 8 wt.-%, preferably 0.2 wt.- % to 4 wt.-%,
(c) the amount of the organic liquid having a boiling point below 120 °C is in the range of from 70 wt.-% to 99.5 wt.-%, preferably 88 wt.-% to 99 wt.-%,
(d) the total amount of polymerizable moieties is in the range of from 0.0005 wt.-% to 4.9 wt.-%, preferably 0.025 wt.-% to 1.04 wt.-%,
(e) the total amount of initiators (if present) is in the range of from 0.00001 wt.-% to 0.06 wt.-%, preferably 0.0001 wt.-% to 0.02 wt.-%,
(f) the total amount of said polymers is in the range of from 0 wt.-% to 4.9 wt.-%, preferably 0.025 wt.-% to 1.04 wt.-%,
(g) the amount of the aprotic organic liquid having a boiling point of 120 °C or higher is in the range of from 0.00009 wt.-% to 0.8 wt.-%, preferably 0.005 wt.-% to 0.7 wt.%,
(h) the total amount of said electrolytes as defined above is in the range of from 0 wt.- % to 0.3 wt.-%, preferably 0 wt.-% to 0.075 wt.-%,
(i) the total amount of electronically conductive nanoobjects as defined above is in the range of from 0 wt.-% to 0.9 wt.-%, preferably 0 wt.-% to 0.4 wt.-%,
in each case based on the total weight of the composition.
When said polymerizable moieties are co-polymerizable monomers selected from the group consisting of alkyi acrylates and alkyi methacrylates and from the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates, the total amount of monomers selected from the group consisting of alkyi acrylates and alkyi methacrylates is in the range of from 0.0004 wt.-% to 4.0 wt.-%, preferably 0.02 wt.-% to 0.84 wt.-%, and the total amount of monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates is in the range of from 0.0001 wt.-% to 0.9 wt.-%, preferably 0.005 wt.-% to 0.2 wt.- %.
Preferably, in said composition, the ratio between
(a) the total weight of said nanoobjects comprising one or more electrochromic oxides of tungsten and
(i) the total weight of said electronically conductive nanoobjects as defined above (if present)
is in the range of from 1 to 1000, preferably 5 to 300. At a weight ratio above 1000, in an electrochromic composite layer prepared from a composition according to the invention, the amount of electronically conductive nanoobjects (i) may be not sufficient to have a remarkable effect on the electronic conductivity. On the other hand, at a weight ratio below 1 , in an electrochromic composite layer prepared from a composition according to the invention the amount of nanoobjects (a) comprising one or more oxides of tungsten as defined above may be not sufficient for achieving an appropriate electrochromic effect.
Further preferably, the ratio between
(a) the total weight of said nanoobjects comprising one or more oxides of tungsten and
(h) the total weight of said electrolytes (if present)
is in the range of from 0.5 to 330000, preferably 6.67 to 9000.
At a weight ratio above 330000, in an electrochromic composite layer prepared from a composition according to the invention the amount of electrolytes (h) may be not sufficient for achieving an appropriate ionic conductivity. On the other hand, at a weight ratio below 0.5, in an electrochromic composite layer prepared from a composition according to the invention the amount of nanoobjects (a) comprising one or more oxides of tungsten as defined above may be not sufficient for achieving an appropriate electrochromic effect.
Further preferably, the ratio between
(g) the weight of said aprotic organic liquid having a boiling point of 120 °C or higher and
(h) the total weight of said electrolytes (if present)
is in the range of from 0.0003 to 104000, preferably 0.07 to 100.
At a weight ratio below 0.0003, the amount of the aprotic organic liquid (g) in an electrochromic composite layer prepared from a composition according to the invention may be not sufficient for dissolving the electrolytes (h). On the other hand, at a weight ratio above 104000, the amount of electrolytes (h) in an electrochromic composite layer prepared from a composition according to the invention may be not sufficient to achieve an appropriate ionic conductivity if there is no migration or diffusion of ions of an electrolyte (h) as defined above from another source into said layer.
Further preferably, the ratio between
(d) the total weight of said polymerizable moieties
and the total weight of
(a) said nanoobjects comprising one or more oxides of tungsten
(g) said aprotic organic liquid having a boiling point of 120 °C or higher
(h) said electrolytes (if present)
(i) said electronically conductive nanoobjects as defined above (if present) is in the range of from 0.00002 to 49, preferably 0.018 to 2.06.
At a weight ratio below 0.00002, the amount of polymerizable moieties in the composition may be not sufficient for forming a matrix which is capable of binding and accommodating the constituents (a), (g), (h) and (i) as described above when an electrochromic composite layer is prepared from a composition according to the invention. On the other hand, at a weight ratio above 49, the amount of the constituents (a), (g), (h) and (i), which determine the electrochromic effect and other important properties of an electrochromic composite layer prepared from a composition according to the present invention may be not sufficient to achieve the desired properties.
Further preferably the ratio between the weight of said carrier liquid having a boiling point below 120 °C
and
(a) the total weight of nanoobjects comprising one or more oxides of tungsten is in the range of from 3.5 to 1075, preferably 8.8 to 206.
At a weight ratio below 3.5, the fraction of solids in the composition is quite high, which may impede application of the composition by means of wet processing techniques. On the other hand, at a weight ratio above 1075, the fraction of the carrier liquid, which has to be removed in the process of forming an electrochromic composite layer, is relatively large, and processing may become inefficient.
Further preferably the weight ratio between
(b) water
and
(c) said organic liquid having a boiling point below 120 °C
is in the range of from 0.0004 to 0.1 1 , preferably 0.002 to 0.045.
At a weight ratio below 0.0004, the fraction of water in the carrier liquid is quite low and may be not sufficient to achieve the desired effect. On the other hand, at a weight ratio above 0.1 1 , the fraction of said organic liquid having a boiling point below 120 °C in the carrier liquid is quite low and may be not sufficient to achieve the desired effect
In a specifically preferred composition according to the present invention,
(a) said nanoobjects are nanoparticles comprising one or more oxides of tungsten, preferably consisting of one or more oxides of tungsten
(c) said organic liquid having a boiling point below 120 °C is selected from the group consisting of ethanol, methanol, 2-propanol, 2-methyl tetrahydrofuran and mixtures thereof
(d) said polymerizable moieties are one or more kinds of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more kinds of monomers selected from the group consisting of hydroxyalkyl acrylates and hydrox- yalkyl methacrylates
(e) if present, said initiator is an initiator which decomposes into radicals when exposed to irradiation
(g) said aprotic organic liquid is selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2- propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
(h) if present, said at least one electrolyte is selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sulfonimide and lithium bis(fluorosulfonyl)imide (i) if present, said electronically conductive nanoobjects are nanowires comprising, preferably consisting of materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel, preferably silver nanowires.
Optionally said specifically preferred composition according to the present invention further comprises
(e) one or more initiators for initiating radical polymerization of said co-polymerizable monomers (d).
Preferably said polymerizable monomers are butyl acrylate and hydroxybutyl acrylate.
For preferred concentration ranges and weight ratios of the constituents of the above-described specifically preferred composition according to the present invention, reference is made to the disclosure provided above.
A second aspect of the present invention relates to a process for preparing a composite layer as defined above on a surface of a solid substrate,
said process comprising the steps of
forming on a surface of said solid substrate a wet film by applying a composition according to the first aspect of the present invention to said surface of said solid substrate
removing said constituents (b) and (c) of said composition from the wet film formed on said surface of said solid substrate
polymerizing the polymerizable moieties (d) on said surface of said solid substrate.
Particularly preferably, the composition applied to said surface of said solid substrate comprises
(d) one or more polymerizable moieties,
and
(e) one or more initiators for initiating radical polymerization of said polymerizable moieties. Polymerization of the polymerizable moieties is preferably initiated by irradiation, especially irradiation having a wavelength in the range of from 360 nm to 420 nm, in the presence of an initiator which decomposes into radicals when exposed to said irradiation. Suitable initiators are known in the art and are commercially available. In certain cases, preparing said process further comprises the step of annealing the layer formed on the surface of the solid substrate after polymerizing the polymerizable monomers.
Said solid substrate comprises, preferably consists of, one or more materials selected from the group consisting of glasses, metals, transparent conducting oxides and organic poly- mers.
In some cases, the surface of the solid substrate to which the composition according to the invention is applied comprises an electronically conductive material, preferably an optically transparent electronically conductive material. Preferred optically transparent conducting materials are transparent conducting oxides (TCO), preferably selected from the group consisting of ITO (indium doped tin oxide), AZO (aluminum doped zinc oxide), IGZO (indium gallium doped zinc oxide), GZO (gallium doped zinc oxide), FTO (fluorine doped tin oxide), indium oxide, tin oxide and zinc oxide. In some cases, the surface of the solid substrate layer upon which the electrochromic composite layer is arranged comprises one or more metallic electronically conductive materials, wherein the metals are preferably se- lected from the group consisting of Cu, Ag, Au, Pt and Pd. Preferably, the metal at the solid substrate surface is present in the form of a structure which is optically transparent, e.g. in the form of fine mesh or nanowires.
However, it has been found that in cases where the composition comprises electroconduc- tive nanoobjects (i) as defined above the electronic in-plane conductivity of an electro- chromic composite layer prepared from a composition according to the invention is sufficiently high so that providing the solid substrate surface with an electronically conductive material can be omitted.
Said solid substrate is preferably in a form selected from the group consisting of foils, films, webs, panes and plates.
In certain cases, said solid substrate comprises an organic polymer and has a thickness the range of from 10 μιτι to 200 μιτι, preferably from 50 μιτι to 150 μιτι. In other cases, said solid substrate comprises glass and has a thickness in the range from 3 to 7 mm, preferably 4 to 6 mm, or in the range from 0.5 to 2.5 mm, preferably 0.7 to 2 mm.
Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass. Optionally, the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing away from the above- described composite layer.
Preferred organic polymers are selected from the group consisting of polymethylmethacrylate (PMMA, commercially available e.g. as Plexiglas™), polycarbonate (PC), polyethylene (PE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP), polyethylene therephthalate (PET), glycol modified polyethylene therephthalate, polyethylene naphthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), polyvinyl chloride (PVC), polyimides (PI), pol- ypropyleneoxide (PPO) and mixtures thereof. PET and PEN are particularly preferred. Preferably, said solid substrate has a light transmission of 80 % or more measured according to ASTM D1003 (Procedure A) as published in November 2013.
Preferably, the composition according to the present invention is applied to the surface of said solid substrate by coating or printing, preferably by a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultra- sonic spray-, dip- and blade coating, or by a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing.
Preferably, the wet film formed by applying the composition according to the present invention to said surface of said solid substrate has a thickness in a range of from 1 μητι to 250 μητι, preferably of from 20 μιτι to 150 μιτι. Said thickness is also referred to as "wet thick- ness".
In the above-defined process according to the present invention, the carrier liquid which has a boiling point below 120 °C is removed from said wet film on said surface of said solid substrate by exposing said wet film to a temperature in the range of from 20 °C to 120 °C, preferably 40 °C to 120 °C, most preferably 80 °C to 120 °C. Preferably, the composition which in the process according to the invention is applied to said surface of said solid substrate is selected from the above-defined preferred compositions according to the first aspect of the present invention.
The step of polymerizing the polymerizable moieties on said surface of said solid substrate is performed after the step of removing said carrier liquid having a boiling point below 120 °C from the wet film formed on said surface of said solid substrate. In certain cases, in the step of polymerizing the polymerizable moieties the degree of conversation of the double bonds in the polymerizable moieties is significantly below 96 %, preferably 90 % or less, further preferably 80 % or less, more preferably 70 % or less, particularly preferably 60 % or less, or 50 % or less, and polymerization is completed in a later stage e.g. when the surface of the composite layer facing away from the solid substrate is to be bonded to another layer (see below).
In certain cases, after polymerization of said polymerizable moieties on the surface of said solid substrate, a sequence comprising the steps of
forming a wet film by applying the above-defined composition according to the invention on the surface of the layer wherein the polymerizable moieties have been polymerized,
removing said constituents (b) and (c) of said composition from the wet film, polymerizing said polymerizable moieties in the layer,
optionally annealing the layer after polymerizing the polymerizable monomers is carried out and optionally repeated at least once.
An especially preferred process according to the second aspect of the present invention is a process for preparing a precursor layer of an electrochromic composite layer as defined above on a surface of a solid substrate, said process comprising the steps of
forming on a surface of said solid substrate a wet film by applying a composition which contains the above-defined constituents (a), (b), (c), (d) and (g) and optionally one, more or all of the above-defined constituents (e), (f) and (i) to said surface of said solid substrate
removing said constituents (b) and (c) of said composition from the wet film formed on said surface of said solid substrate
polymerizing the polymerizable moieties (d) on said surface of said solid substrate. Another especially preferred process according to the second aspect of the present invention is a process for preparing an electrochromic composite layer as defined above on a surface of a solid substrate, said process comprising the steps of
forming on a surface of said solid substrate a wet film by applying a composition which contains the above-defined constituents (a), (b), (c), (d), (g) and (h) and optionally one, more or all of the above-defined constituents (e), (f) and (i) to said surface of said solid substrate
removing said constituents (b) and (c) of said composition from the wet film formed on said surface of said solid substrate
polymerizing the polymerizable moieties (d) on said surface of said solid substrate.
Preferably, in a process for preparing a composite layer as defined above, the following constituents of the composition according to the first aspect of the present invention are applied to the surface of said solid substrate in the following amount per cm2 of said surface:
(a) nanoobjects comprising one or more oxides of tungsten as defined above in an amount of 0.05 mg/cm2 to 2 mg/cm2
(d) polymerizable moieties in an amount of 0.00024 mg/cm2 to 4.14 mg/cm2
(f) optionally polymers in an amount of 0.00024 mg/cm2 to 4.14 mg/cm2
(g) the aprotic organic liquid having a boiling point of 120 °C or higher in an amount of 0.00004 mg/cm2 to 0.64 mg/cm2
(h) optionally electrolytes having cations selected from the group consisting of H+, Li+, Na+, K+ in an amount of 0.000006 mg/cm2 to 0.1 mg/cm2
(i) optionally electronically conductive nanoobjects not comprising any oxides of tungsten in an amount of 0.00005 mg/cm2 to 2 mg/cm2.
When said polymerizable moieties are co-polymerizable monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and from the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates, said monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates are applied in an amount of 0.0006 mg/cm2 to 10.9 mg/cm2 and said monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates in an amount of 0.0001 mg cm2 to 2.4 mg /cm2.
A third aspect of the present invention relates to the use of a composition according to the first aspect of the present invention for preparing a layer comprising a matrix formed of one or more kinds of organic polymers
and dispersed within said matrix
(a) nanoobjects comprising one or more oxides of tungsten
(g) an aprotic organic liquid having a boiling point of 120 °C or higher
(h) optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g) on a surface of a solid substrate.
Preferably, the composition used herein is selected from the above-defined preferred compositions according to the first aspect of the present invention. It is noted that a composition according to the first aspect of the present invention may also be used for preparing any other objects and formulations comprising nanoobjects (a) as defined above.
A fourth aspect of the present invention relates to a process for preparing an article comprising a solid substrate having a surface and, arranged on said surface of said solid sub- strate, an electrochromic composite layer or a precursor layer thereof as defined above. Said process comprises preparing a composite layer as defined above on a surface of a solid substrate by a process as described above in the context of the second aspect of the present invention.
Preferably, said solid substrate comprises one or more materials selected from the group consisting of glasses, metals, transparent conducting oxides and organic polymers. Said solid substrate is preferably in a form selected from the group consisting of foils, films, webs, panes and plates. Preferably said solid substrate is optically transparent, i.e. exhibits a light transmission of 80 % or more measured according to DIN EN 410. Regarding further specific and preferred features of the solid substrate, reference is made to the disclosure provided above in the context of the second aspect of the present invention.
The above-defined layer is arranged on a surface of said solid substrate in such manner that it partially or completely covers a surface of said solid substrate. In specific cases the layer forms a pattern on said surface of said solid substrate. The pattern may be selected from any random and non-random structures, like grids, stripes, waves, dots and circles. The above-defined layer arranged on the surface of the solid substrate has a thickness in the range of from 0.05 μιτι to 500 μιτι, preferably 0.05 μιτι to 50 μιτι, most preferably 0.1 μιτι to 30 μηη.
In a preferred article said composite layer comprises
a matrix formed of one or more organic polymers which are copolymerization products of one or more monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more monomers selected from the group of hy- droxyalkyl acrylates and hydroxyalkyl methacrylates
and dispersed within said matrix
(a) nanoparticles comprising one or more oxides of tungsten, preferably consisting of one or more oxides of tungsten,
(g) an aprotic organic liquid selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
(h) optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g).
In certain cases, said composite layer further comprises
(i) nanowires comprising, preferably consisting of, materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel
dispersed within said matrix formed of one or more organic polymers which are copolymerization products of one or more monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates.
If any electrolytes (h) as defined above are present in said composite layer, it is an electro- chromic composite layer as defined above. If no electrolytes (h) as defined above are present in said composite layer, it is a precursor layer as defined above. In certain cases, an article obtainable according to the fourth aspect of the present invention consists of the above-defined solid substrate and the above-defined layer arranged on a surface of said solid substrate.
In other cases, an article obtainable according to the fourth aspect of the present invention contains further layers which may serve specific functions.
A specifically preferred article obtainable according to the fourth aspect of the present invention comprises a multilayer structure suitable for production of or use in an electrochromic device. The term "electrochromic device" as used herein refers to a device exploiting the electrochromic effect as defined above. Such device comprises at least one elec- trode comprising an electrochromic material, a counter electrode and a separator layer sandwiched between and electronically separating said electrodes. Electrochromic devices are used, inter alia, as fagade and roof elements, interior construction and design elements for buildings and vehicles, displays, visualization optics and electrochromic mirrors. A widely known type of electrochromic devices are so-called smart windows. The term "smart windows" is known in the art.
Such preferred article for production of or use in an electrochromic device comprises a first solid substrate having a surface
arranged on said surface of said first solid substrate, a composite layer as defined above
- a separator layer disposed on the surface of the composite layer facing away from the solid substrate.
Such preferred article is obtainable by a process comprising the steps of
preparing a composite layer as defined above on a surface of a solid substrate by a process as described above in the context of the second aspect of the present in- vention, and
disposing a separator layer on the surface of said composite layer facing away from the solid substrate. Said separator layer is virtually electronically insulating but allows for flow of ions. For further details, see below.
Another preferred article for production of or use in an electrochromic device comprises a first solid substrate having a surface
arranged on said surface of said first solid substrate, a composite layer as defined above
a second solid substrate having a surface
arranged on said surface of said second solid substrate, a counter electrode layer a separator layer sandwiched between and electronically separating said composite layer and said counter electrode layer.
Said article comprises a multilayer structure which in the direction of stacking consists of a first solid substrate, a composite layer as defined above, a separator layer, a counter electrode layer and a second solid substrate.
In said article, said separator layer has a first surface and a second surface opposite to said first surface, wherein said first surface of said separator layer is in contact with a surface of said composite layer facing away from said first solid substrate, and said second surface of said separator layer is in contact with a surface of said counter electrode layer facing away from said second solid substrate.
Said separator layer is virtually electronically insulating and electronically separates the composite layer and the counter electrode but allows for flow of ions between the composite layer and the counter electrode. Suitable separator layers are known in the art.
Said separator layer preferably has a thickness in the range of from 0.05 μιτι to 1500 μιτι, preferably 0.05 μιτι to 1000 μιτι, most preferably 1 μητι to 800 μιτι. Thickness may be determined by profilometry, atomic force microscopy or electron microscopy.
Preferably, in said article for production of or use in an electrochromic device at least one of said solid substrates has a light transmission of 80 % or more measured according to DIN EN 410. An article comprising the above-defined multilayer structure is obtainable by a process comprising the steps of
preparing
a first layer assembly comprising a first solid substrate having a surface and arranged on said surface of said first solid substrate a composite layer as defined above, and optionally a separator layer disposed on a surface of said composite layer facing away from said first solid substrate or a wet film obtained by applying a composition suitable for forming a separator layer on said surface of the first composite layer facing away from said first solid substrate, and
a second layer assembly comprising a second solid substrate having a surface and arranged on said surface of said second solid substrate a counter electrode layer, and optionally a separator layer disposed on a surface of said counter electrode layer facing away from said second solid substrate or a wet film obtained by applying a composition suitable for forming a separator layer on said surface of the counter electrode layer facing away from said second solid substrate,
with the proviso that at least one of said first and second layer assembly comprises a separator layer or a wet film as defined above
- stacking and bonding said layer assemblies so that an article is obtained having a separator layer sandwiched between said first composite layer and said counter electrode layer.
Preferably, in said article for production of or use in an electrochromic device, said separator layer comprises
- a matrix formed of one or more organic polymers
and dispersed within said matrix
(g") an aprotic organic liquid having a boiling point of 120 °C or higher,
(h") optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g"). Accordingly, disposing a separator layer on the surface of said composite layer facing away from said first solid substrate and/or on the surface of said counter electrode layer facing away from said second solid substrate preferably comprises the steps of forming on said surface of said composite layer resp. said counter electrode layer a wet film by applying to said surface a composition comprising
(c") optionally a carrier liquid having a boiling point below 120 °C
(d") one or more kinds of polymerizable moieties,
(e") optionally one or more initiators for initiating radical polymerization of said one or more kinds of polymerizable moieties
(g") an aprotic organic liquid having a boiling point of 120 °C or higher
(h") optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+
in case the composition contains a carrier liquid (c") having a boiling point below 120 °C, removing the carrier liquid having a boiling point below 120 °C from the wet film formed on the surface of said composite layer resp. said counter electrode layer polymerizing the polymerizable moieties in the layer formed on the surface of said composite layer resp. said counter electrode layer.
In certain cases, said composition for preparing the separator layer comprises a carrier liquid. However, in said composition for disposing a separator layer as defined above advantageously a carrier liquid as a vehicle for wet processing can be omitted, because said composition does not comprise non-dissolved matter, in contrast to the above-described composition for preparing an electrochromic composite layer or a precursor layer thereof. Accordingly, the step of removing the carrier liquid from the wet film can be omitted in preparing the separator layer.
Regarding preferred and specific carrier liquids (c"), polymerizable moieties (d"), initiators (e"), aprotic organic liquids (g") having a boiling point of 120 °C or higher and electrolytes (h"), the same applies as disclosed above in the context of the first aspect of the present invention for the carrier liquid (c), polymerizable moieties (d), initiators (e), aprotic organic liquid (g) having a boiling point of 120 °C or higher and electrolytes (h), resp., of the composition according to the first aspect of the present invention.
In the composition for preparing the separator layer, preferably the polymerizable moieties (d") are the same as the polymerizable moieties (d) in the composition for preparing the composite layer, the aprotic organic liquid (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the composition for preparing the composite layer, and - if present - the electrolyte (h") is the same as the electrolyte (h) in the composition for preparing the composite layer.
Accordingly, in said separator layer, preferably the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer and - if present - the electrolyte (h") is the same as the electrolyte (h) in the first composite layer.
Without being bound to theory, it is believed that in the separator layer of the electrochromic device according to the present invention said aprotic organic liquid (g") including said dis- solved electrolytes (h") as defined above is confined within pores extending through the matrix, thus providing a network for the transport of ions across the separator layer.
Water may also provide for ionic conductivity of the separator layer. A separator layer comprising water is obtainable by using a carrier liquid (c") consisting of water and another liquid having a boiling point of less than 120 °C. The amount of water that remains in said system consisting of water and two other liquids (said constituent of the carrier liquid having a boiling point of less than 120 °C and the aprotic organic liquid (g") having a boiling point of 120 °C or higher as defined above) can be estimated according to Raoult's law or can be determined from experimental data, as known by the skilled person. However, in the context of this disclosure, water is not an electrolyte (h") as defined above. If said composition for preparing the separator layer comprises a carrier liquid, the step of polymerizing the polymerizable moieties is performed after the step of removing said carrier liquid having a boiling point below 120 °C from the wet film formed on said surface of said solid substrate. In certain cases, in the step of polymerizing the polymerizable moieties the degree of conversation of the double bonds in the polymerizable moieties is signif- icantly below 96 %, preferably 90 % or less, further preferably 80 % or less, more preferably 70 % or less, particularly preferably 60 % or less, or 50 % or less, and polymerization is completed in a later stage e.g. for bonding the surface of the separator layer facing away from the composite layer to another layer (see below).
In certain cases, after polymerization of said polymerizable moieties on the surface of said composite layer, a sequence comprising the steps of
forming a wet film by applying the above-defined composition on the surface of the layer wherein the polymerizable moieties have been polymerized, in case the composition contains a carrier liquid (c") removing from said wet film said carrier liquid having a boiling point below 120 °C,
polymerizing said polymerizable moieties in the layer,
is carried out and optionally repeated at least once. Preferably, the composition for preparing the separator layer is applied to the surface of said composite layer by coating or printing, preferably by a coating technique selected from the group consisting of roll-to-roll-, roll-to-sheet-, sheet-to-sheet-, slot-die-, spray-, ultrasonic spray-, dip- and blade coating, or by a printing technique selected from the group consisting of ink-jet-, pad-, offset-, gravure-, screen-, intaglio- and sheet-to-sheet- printing. In the above-defined process for disposing the separator layer, the carrier liquid (c") - if present - is removed from said wet film on said surface of said solid substrate by exposing said wet film to a temperature in the range of from 20 °C to 120 °C, preferably 40 °C to 120 °C, most preferably 80 °C to 120 °C.
Preferably, the composition for preparing the separator layer does not contain a carrier liquid (c"), and the wet film formed by applying the composition for preparing the separator layer to said surface of said composite layer has a thickness in a range of from 0.05 μιτι to 1500 μιτι, preferably of from 0.05 μιτι to 1000 μιτι. Said thickness is also referred to as "wet thickness".
For further details of disposing a separator layer on the surface of said composite layer facing away from said first solid substrate and/or on the surface of said counter electrode layer facing away from said second solid substrate, see the non-prepublished patent application having the application number PCT/EP2017/055320.
Said counter electrode layer comprises an electroactive material capable of repeatedly inserting and releasing ions to compensate for changes of the oxidation state of the metal of the electrochromic oxide in the nanoobjects (a) present in the electrochromic composite layer. Upon operation of the electrochromic device the electrochromic composite layer and the counter electrode layer are connected to a direct voltage source. Between the electrochromic composite layer and the counter electrode, virtually no electrons are transferred across the separator layer. Said counter electrode layer may comprise an electroactive material which independent from its state of oxidation is substantially optically transparent or has an electrochromic effect involving a color change significantly less pronounced than that of the electrochromic metal oxide in the nanoobjects (a) of the electrochromic composite layer. Suitable electro- active materials are known in the art and include, but are not limited to tin oxide, cerium oxide, and transparent polymers capable of intercalating lithium ions. Alternatively, said counter electrode layer comprises an electroactive material which exhibits an electrochromic effect having a dependence on the applied electrochemical potential which is opposite to the electrochromic effect of tungsten oxide.
For instance, the counter electrode layer is obtained by depositing an electroactive material on the surface of said second solid substrate. Depositing the electroactive material (e.g. an electrochromic material) may be achieved by means of sputtering.
Preferably said counter electrode layer comprises one or more oxides of nickel.
In case the counter electrode does not contain any electrolyte, at least one of the composition according to the first aspect of the present invention (which is used for preparing the composite layer) and the composition for preparing the separator layer must contain an electrolyte (h), (h"), resp.
Preferably, in said article for production of or use in an electrochromic device, said counter electrode layer is a second composite layer comprising
a matrix formed of one or more organic polymers
and dispersed within said matrix
(a') nanoobjects comprising one or more electrochromic compounds selected from the group consisting of oxides of elements selected from the group consisting of transition metals, rare earth elements, and elements of groups 12, 13 and 14 with the exception of carbon and tungsten
(g') an aprotic organic liquid having a boiling point of 120 °C or higher,
(h') optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g'). In certain cases, said second composite layer further comprises
(i') electronically conductive nanoobjects not comprising any compounds selected from the group consisting of oxides of elements selected from the group consisting of transition metals, rare earth elements, and elements of groups 12, 13 and 14 dispersed within said matrix formed of one or more organic polymers.
As used herein, "elements of groups 12, 13 and 14" refer to elements of groups 12, 13 and 14 of the periodic table of the elements according to lUPAC notation.
Preferably, said electroconductive nanoobjects (i') are nanowires comprising, preferably consisting of, materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel.
Accordingly, said article comprises a first composite layer arranged on a surface of said first solid substrate, and a second composite layer arranged on a surface of said second solid substrate. Said article comprises a multilayer structure which in the direction of stack- ing consists of a first solid substrate, a first composite layer as defined above, a separator layer, a second composite layer as defined above and a second solid substrate. In said article said separator layer has a first surface and a second surface opposite to said first surface, wherein said first surface of said separator layer is in contact with a surface of said first composite layer facing away from said first solid substrate, and said second surface of said separator layer is in contact with a surface of said second composite layer facing away from said second solid substrate.
In said second composite layer, the nanoobjects (a') comprise electrochromic compounds which are different from the electrochromic oxides of tungsten comprised by the nanoobjects (a) of the first composite layer. As regards criteria for selecting said electrochromic material, see above. In a specific preferred case, the nanoobjects (a) of the first composite layer comprise one or more oxides of tungsten, and the nanoobjects (a') of the second composite layer comprise one or more oxides of nickel.
In said second composite layer, preferably the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g') having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer, and - if present - the electrolyte (h') is the same as the electrolyte (h) in the first composite layer. Such preferred article for production of or use in an electrochromic device is obtainable by a process comprising the steps of
preparing
a first layer assembly comprising a first solid substrate having a surface and arranged on said surface of said first solid substrate a first composite layer as defined above, and optionally a separator layer disposed on a surface of said first composite layer facing away from said first solid substrate or a wet film obtained by applying the above-described composition for forming a separator layer on said surface of the first composite layer facing away from said first solid substrate, and
a second layer assembly comprising a second solid substrate having a surface and arranged on said surface of said second solid substrate a second composite layer as defined above, and optionally a separator layer disposed on a surface of said second composite layer facing away from said second solid substrate or a wet film obtained by applying the above-defined composition for forming a separator layer on said surface of the second composite layer facing away from said second solid substrate,
with the proviso that at least one of said first and second layer assembly comprises a separator layer or a wet film as defined above
- stacking and bonding said layer assemblies so that an article is obtained having a separator layer sandwiched between said first composite layer and said second composite layer.
In this process, a bonding is achieved between the separator layer of the first layer assembly and the second composite layer, resp. between the separator layer of the second layer assembly and the first composite layer, resp. between the separator layer of the first layer assembly and the separator layer of the second layer assembly. For further details, see the non-prepublished patent application having the application number PCT/EP2017/055320.
Bonding may be achieved by polymerizing the monomers (d") in said wet film obtained by applying the above-defined composition for preparing a separator layer on the surface of the first resp. second composite layer as defined above, or by completing the polymerization of the polymerizable moieties (d), (d'), (d"), resp. in said layers to be bonded.
More preferably, in said article for production of or use in an electrochromic device, said counter electrode layer is a second composite layer as defined above and said separator layer comprises
a matrix formed of one or more organic polymers
and dispersed within said matrix
(g") an aprotic organic liquid having a boiling point of 120 °C or higher,
(h") optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g").
Disposing a separator layer on the surface of said first composite layer facing away from said first solid substrate and/or on the surface of said second composite layer facing away from said second solid substrate comprises the steps as described above.
In said second composite layer and said separator layer, preferably the matrix is formed of the same organic polymers as the matrix in the first composite layer, the aprotic organic liquid (g') resp. (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the first composite layer, and - if present - the electrolyte (h') resp. (h") is the same as the electrolyte (h) in the first composite layer.
Accordingly, in the composition for preparing the second composite layer and in the composition for preparing the separator layer, preferably the polymerizable moieties (d') resp. (d") are the same as the polymerizable moieties (d) in the composition for preparing the first composite layer, the aprotic organic liquid (g') resp. (g") having a boiling point of 120 °C or higher is the same as the aprotic organic liquid (g) in the composition for preparing the first composite layer, and - if present - the electrolyte (h') resp. (h") is the same as the electrolyte (h) in the composition for preparing the first composite layer.
It is noted that in an article for production of or use in an electrochromic device comprising a first composite layer as defined above and one or both of a separator layer as defined above and a second composite layer as defined above, at least one of said layers must contain an electrolyte (h), (h'), (h"), resp. It has been found that ions from the electrolyte which is present in one of said layers may enter the other layer(s) by diffusion and migration, thereby providing for sufficient ionic conductivity across the respective layers.
Accordingly, at least one of the composition according to the first aspect of the present invention (which is used for preparing the first composite layer), the composition for preparing the separator layer and the composition for preparing the second composite layer must contain an electrolyte (h), (h'), (h"), resp. Water may also provide for ionic conductivity of the composite layers and the separator layer, as explained above. However, in the context of this disclosure, water is not an electrolyte (h), (h'), (h") as defined above.
A specifically preferred article for production of or use in an electrochromic device com- prises
a first solid substrate having a surface
arranged on said surface of said first solid substrate, a first composite layer a second solid substrate having a surface
arranged on said surface of said second solid substrate, a second composite layer - a separator layer interfacing and electronically separating said first composite layer and said second composite layer.
wherein
said first composite layer comprises
a matrix formed of one or more organic polymers
- and dispersed within said matrix
(a) nanoobjects comprising one or more electrochromic oxides of tungsten
(g) an aprotic organic liquid having a boiling point of 120 °C or higher,
(h) optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g) and
said second composite layer comprises
a matrix formed of one or more organic polymers and dispersed within said matrix (a') nanoobjects comprising one or more electrochromic oxides of nickel (g') an aprotic organic liquid having a boiling point of 120 °C or higher, (h') optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g').
Further preferably, in said specifically preferred article for production of or use in an elec- trochromic device said first composite layer comprises
a matrix formed of one or more organic polymers which are copolymerization products of one or more monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more monomers selected from the group of hy- droxyalkyl acrylates and hydroxyalkyl methacrylates
and dispersed within said matrix
(a) nanoparticles comprising one or more oxides of tungsten
(g) an aprotic organic liquid selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
(h) optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g)
and said second composite layer comprises
a matrix formed of one or more organic polymers which are copolymerization products of one or more monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more monomers selected from the group of hydroxyalkyl acrylates and hydroxyalkyl methacrylates
and dispersed within said matrix
(a') nanoparticles comprising one or more oxides of nickel
(b') optionally one or more salts selected from the group consisting of scandium bis(trifluoromethane)sulfonimide, yttrium bis(trifluoromethane)sulfonimide, aluminum bis(trifluoromethane)sulfonimide, lanthanum bis(trifluoro- methane)sulfonimide, cerium bis(trifluoromethane)sulfonimide, nickel bis(fluorosulfonyl)imide, copper bis(fluorosulfonyl)imide, zinc bis(fluorosul- fonyl)imide, yttrium trifluoromethylsulfonate, aluminum trifluoromethylsulfonate, lanthanum trifluoromethylsulfonate, cerium trifluoromethylsulfonate, and yttrium fluorosulfonate (g') an aprotic organic liquid selected from the group consisting of ethanol, methanol, 2-propanol, 2-methyl tetrahydrofuran and mixtures thereof
(h') optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide dissolved in said aprotic organic liquid (g").
The second composite layer of the above-defined specifically preferred article is obtainable using the composition or according to the process described in a patent application filed by the same applicant on the same day as the present application.
In certain cases, an article for production of or use in an electrochromic device further comprises a support layer attached to the surface of the first solid substrate facing away from the composite layer and/or a support layer attached to the surface of the second solid substrate facing away from said counter electrode layer. Preferably, a first support layer is attached to the surface of the first solid substrate facing away from the composite layer and a second support layer is attached to the surface of the second solid substrate facing away from said counter electrode layer. In this regard, it is particularly preferred that the first and second solid substrate comprise materials from the group of organic polymers and are in the form of foils, films, webs, and the first and second support layer comprise glass.
Furthermore, a third support layer may be attached to the surface of the first support layer facing away from the first solid substrate and/or a fourth support layer may be attached to the surface of the second support layer facing away from the second solid substrate. In this regard it is particularly preferred that a third support layer is attached to the surface of the first support layer facing away from the first solid substrate and a fourth support layer is attached to the surface of the second support layer facing away from the second solid substrate. In this regard, it is particularly preferred that the first, second, third and fourth support layer comprise glass.
Said support layers comprise one or more materials selected from the group consisting of glasses, metals and organic polymers. Preferred types of glass are e.g. float glass, low iron float glass, heat strengthened glass and chemically strengthened glass. Optionally, the glass has a low-emissivity (low-e) coating, sun-protection coating or any other coating on the surface facing outwardly. Attaching said first resp. second support layer to said first resp. second solid substrate preferably comprises applying an adhesive between the support layer and the surface of the solid substrate to which said support layer has to be attached. Attaching said third resp. fourth support layer to said first resp. second support layer preferably comprises applying an adhesive. Suitable adhesives are thermoplastics, e.g. polyvinylbutyral, polyvinylalcohol, polyvinylacetate, ethylene-vinylacetate-copolymers, polyurethanes, ionomer resins (commercially available e.g. under the trade name SentryGlas®) and polymethylmethacrylate (PMMA).
The present invention further relates to the use of an article as defined above resp., an electrochromic device as defined above in buildings, furniture, cars, trains, planes and ships as well as to the in facades, skylights, glass roofs, stair treads, glass bridges, canopies, railings, car glazing, train glazing.
The present invention further relates to insulating glass units, windows, rotating windows, turn windows, tilt windows, top-hung windows, swinging windows, box windows, horizontal sliding windows, vertical sliding windows, quarterlights, store windows, skylights, light domes, doors, horizontal sliding doors in double-skin facades, closed cavity facades, all- glass constructions, D3-facades (Dual, Dynamic Durable Facade), facade glass construction elements (e.g. but not limited to fins, louvres), interactive facades (facades reacting on an external impulse e.g. but not limited to a motion control, a radio sensor, other sensors) curved glazing, formed glazing, 3D three-dimensional glazing, wood-glass combinations, over head glazing, roof glazing, bus stops, shower wall, indoor walls, indoor separating elements in open space offices and rooms, outdoor walls, stair treads, glass bridges, canopies, railings, aquaria, balconies, privacy glass and figured glass.
The present invention further relates to thermal insulation, i.e. insulation against heat, in- sulation against cold, sound insulation, shading and/or sight protection. The present invention is preferably useful when combined with further glass layers to an insulation glass unit (IGU), which can be used for building facades. The IGU might have a double (Pane 1 + Pane 2), or triple glazing (Pane 1 + Pane 2 + Pane 3), or more panes. The panes might have different thicknesses and different sizes. The panes might be of tempered glass, tem- pered safety glass, laminated glass, laminated tempered glass, safety glass. The device according to the present application may be used in any of the panes 1 , 2, 3. Materials can be put into the space between the panes. For example, but not limited such materials might be argon, xenon, nitrogen, wooden objects, metal objects, expanded metal, prismatic objects, blinds, louvres, light guiding objects, light guiding films, light guiding blinds, 3-D light guiding objects, sun protecting blinds, movable blinds, roller blinds, roller blinds from films, translucent materials, capillary objects, honey comb objects, micro blinds, micro lamella, micro shade, micro mirrors insulation materials, aerogel, integrated vacuum insulation panels, holographic elements, integrated photovoltaics or combinations thereof.
The present invention further relates to the use in heat-mirror glazing, vacuum glazing, multiple glazing and laminated safety glass.
The present invention further relates to the use in transportation units, preferably in boats, in vessels, in spacecrafts, in aircrafts, in helicopters, in trains, in automotive, in trucks, in cars e.g. but not limited to windows, separating walls, light surfaces and background lighting, signage, pass protection, as sunroof.
The present invention is preferentially useful when combined with further glass layers to an insulation glass unit (IGU), which can be used for building facades.
The invention is now further illustrated by means of non-limiting examples.
Examples
All compositions were obtained in an analogous manner as in the examples in WO 2016/128133. The nanoparticles were either commercially available. All other constituents were all commercially available.
The dispersion stability of the compositions was evaluated as follows: A composition was considered instable if there was a phase separation after two hours such that there was a clear supernatant of 30 % or more in height regarding to the total filling height.
A composition according to the first aspect of the present invention comprising
(a) nanoparticles comprising tungsten oxide (obtained from company Nanograde)
(b) water
(c) 2-propanol
(d) a monomer selected from the group consisting of alkyl acrylates and alkyl methac- rylates and a monomer selected from the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates
(e) an initiator for initiating copolymerization of monomers (d) by UV irradiation (g) 1 ,2-propylene carbonate
was prepared. The concentrations of all constituents were in the above-defined preferred ranges.
For comparison, compositions 1 to 15 comprising the above-defined constituents (a), (c), (d), (e) and (g) and a commercially available dispersing agent (for details, see table 1 ) instead of water were prepared. The concentration of constituents (a), (d), (e) and (g) was the same as in the composition according to the invention.
In pretests, the dispersing agents used for the comparison compositions were found to be able to prevent agglomeration and settling of dispersed nanoparticles (a) as defined above in a composition comprising a carrier liquid selected from ethanol and 2-propanol and none of above-defined components (d), (e) and (g) at least for a couple of hours. As usual, the specific composition of the commercially available dispersing agents was not disclosed by the suppliers. For this reason, in table 1 certain dispersing agents are identified by their trade names. The agglomeration behavior of the composition according to the invention and the comparison compositions was monitored as described above. Only few of the comparison compositions met the above-defined condition of stability.
The composition according to the invention and comparison compositions 10-15 which exhibited no significant agglomeration and settling over two hours were used as inks for preparing composite layers as defined above.
The substrate was in each case a glass plate having a surface coating of indium-tin-oxide (ITO). A wet film was formed in each case by spin-coating the ink on said ITO-coated surface. After evaporation of the carrier liquid at ambient conditions the monomers (d) were copolymerized. The copolymerization was initiated by means of UV irradiation. Thereafter, the coated substrates were heated on a hot plate.
The electrochromic behavior of the composite layers obtained as described above was studied by means of cyclic voltammetry acting as working electrode in the potential range -1.5 V to +1.5 V in a three electrode cell using a 0.5 molar solution of lithium trifluorome- thylsulfonate in 1 ,2-propylene carbonate as the electrolyte, platinum as the counter elec- trade and Ag/Ag+ as the reference electrode. Only the composite layer obtained from the composition according to the invention exhibited reversible electrochromic behavior. It adopted a blue color when the potential was scanned in the cathodic direction and discolored when the potential was scanned back in the anodic direction. In contrast, most of the layers prepared using the comparison compo- sitions did not show any electrochromic effect. In two cases (see table 1 ) a blue color emerged when the potential was scanned in the cathodic direction but did not vanish when the potential was scanned back in the anodic direction.
Table 1
Figure imgf000042_0001
DISPERBYK- coloring but no
10 2-propanol 2164 (supplier: yes yes subsequent disBYK) coloring
BYK-9077 (sup¬
1 1 2-propanol yes yes
plier: BYK)
DISPERBYK-164
12 2-propanol yes yes
(supplier: BYK)
No electrochromic
DISPERBYK-163
13 2-propanol yes yes effect
(supplier: BYK)
DISPERBYK-164
(supplier: BYK) +
14 2-propanol yes yes
BYK-ES 80 (supplier: BYK)
DISPERBYK-163
coloring but no (supplier: BYK) +
15 2-propanol yes yes subsequent disBYK-ES 80 (supcoloring plier: BYK)
coloring and sub¬
2-propanol and
16 none yes yes sequent discolorwater
ing
In addition, the agglomeration behavior of compositions according to the invention comprising the above-defined constituents (a), (b), (c), (d), (e), (g) and an electrolyte (h) (see table 2, concentration in the above-defined preferred range) was monitored. In each case either no visible change or only a slight colloidal turbidity was observed. Table 2
Electrolyte (h) observation
Lithium hexafluorophosphate slight colloidal turbidity
Lithium tetrafluoroborate slight colloidal turbidity
Lithium nitrate slight colloidal turbidity
Lithium bis(fluorosulfonyl)imide no visible change
Lithium bis(trifluoromethane)sulfonimide no visible change
Lithium chloride slight colloidal turbidity
Lithium bromide slight colloidal turbidity Lithium difluorophosphate no visible change
Lithium trifluoromethylsulfonate no visible change
Lithium bis(oxalate)borate slight colloidal turbidity
Lithium difluoro(oxalate)borate slight colloidal turbidity
Lithium perchlorate no visible change
The results show that in a composition according to the invention, agglomeration and settling of the dispersed nanoparticles (a) is effectively suppressed, although said composition comprises constituents (d), (e), (g) and optionally (h) which may have a detrimental influ- ence on the stability of the dispersed nanoparticles (a), as shown in the comparison tests described above. Moreover, a composition according to the invention can be used as an ink for preparing a composite layer which exhibits a reversible electrochromic effect.

Claims
Composition, comprising
(a) nanoobjects comprising one or more oxides of tungsten
(b) water
(c) an organic liquid having a boiling point below 120 °C which is not polymeriza- ble
(d) one or more kinds of polymerizable moieties which are polymerizable by radical polymerization
(e) one or more initiators for initiating radical polymerization of said one or more kinds of polymerizable moieties
(g) an aprotic organic liquid having a boiling point of 120 °C or higher.
Composition according to claim 1 , further comprising
(f) one or more organic polymers
and/or
(h) at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+
and/or
(i) electronically conductive nanoobjects not comprising any oxide of tungsten. Composition according to any preceding claim, wherein
(a) said nanoobjects comprising one or more oxides of tungsten are selected from the group consisting of nanowires and nanoparticles
and/or
(c) said organic liquid having a boiling point below 120 °C is selected from the group consisting of alcohols, amines, carbonic acids, esters, ketones, organic carbonates, polyethers, sulfides and nitriles and mixtures thereof and/or
(d) said polymerizable moieties are selected from the group consisting of alkyl acrylates, alkyl methacrylates, hydroxyalkyl acrylates, hydroxyalkyl methacry- lates, vinyl chloride, vinyl fluoride, acrylonitrile, vinylidene fluoride, vinylidene chloride, hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, tetrahy- drofurane vinylpyrrolidone,
and/or
(f) said organic polymers are selected from the group consisting of polyalkyl acrylates, polyalkyl methacrylates, polyhydroxyalkyl acrylates, poly- hydroxyalkyl methacrylates, polyvinyl chloride, polyvinyl fluoride, polyacrylo- nitrile, polyvinylidene fluoride, polyvinylidene chloride, polyhexafluoropropyl- ene, polytrifluorethylene, polytetrafluoroethylene, polytetrahydrofuran, polyvinylpyrrolidone, polyurethanes, polyethylene oxide
and/or
(g) said non-polymerizable aprotic organic liquid having a boiling point of 120 °C or higher is selected from the group consisting of organic carbonates, alco- holes, amides, carboxylic acid esters, ethers, polyethers, ketones, lactones, lactames, phosphoric acid esters, sulfones, sulfoxides, sulfonates and urea derivatives and mixtures thereof
and/or
(h) said electrolyte is selected from the group consisting of lithium aluminium chloride (LiAICU); lithium hexafluorosilicate (Li2SiF6); lithium hexafluoroantimonate (LiSbFe); LiX(RS02)n wherein n=1 and X=0 or S, n=2 and X=N or P, n=3 and X=C or Si, and R in each case is CmH2m+i-nFn wherein m = 0-20, n = 0-21 ; lithium fluoride (LiF); lithium nitrate (UNO3); lithium perchlorate (LiCIC ); lithium tetrafluoroborate (L1BF4); lithium tetrakis(pentafluorophenyl)borate; lithium difluorophosphate (UPO2F2); lithium hexafluorophosphate (LiPFe); lithium hexafluoroarsenate (LiAsFe); lithium bis(fluorosulfonyl)imide (LiN(S02F)2); lithium trifluoromethylsulfonate (UCF3SO3); LiN(S02CnF2n+i)2 wherein n = 2 to 20; LiC[(CnF2n-i)S02]3 wherein n = 2 to 20; Li(CnF2n+i)S02 wherein n = 2 to 20; lithium bis(trifluoromethane)sulfonimide LiN(CF3S02)2); lithium tris-trifluoro- methyl sulfonylmethide (LiC(CF3S02)3); lithium bisoxalatoborate (LiB(C204)2); lithium difluoro(oxalate)borate (LiBF2(C204)); lithium difluoro(bisoxalato)phos- phate and lithium tetrafluoro(oxalate)phosphate
and/or
(i) said nanoobjects are nanowires comprising materials selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel and alloys of two or more metals selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel.
Composition according to any preceding claim, comprising
(a) nanoparticles comprising one or more oxides of tungsten
(b) water
(c) an organic liquid selected from the group consisting of ethanol, methanol, 2- propanol, 2-methyl tetrahydrofuran and mixtures thereof
(d) one or more kinds of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and one or more kinds of monomers selected from the group consisting of hydroxyalkyi acrylates and hydroxyalkyi methacrylates
(e) an initiator which decomposes into radicals when exposed to irradiation
(g) an aprotic organic liquid selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, 1 ,2-propylene carbonate, fluorinated 1 ,2-propylene carbonate, 1 ,3-propylene carbonate, fluorinated 1 ,3-propylene carbonate and mixtures thereof
(h) optionally at least one electrolyte selected from the group consisting of lithium perchlorate, lithium trifluoromethylsulfonate, lithium bis(trifluoromethane)sul- fonimide and lithium bis(fluorosulfonyl)imide
(i) optionally silver nanowires.
Process for preparing an article comprising a composite layer arranged on a surface of a solid substrate, said composite layer comprising
a matrix formed of one or more kinds of organic polymers
and dispersed within said matrix
(a) nanoobjects comprising one or more oxides of tungsten
(g) an aprotic organic liquid having a boiling point of 120 °C or higher
(h) optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+
said process comprising the steps of
forming on a surface of said solid substrate a wet film by applying a composition according to any of claims 1 to 4 to said surface of said solid substrate removing said constituents (b) and (c) of said composition from the wet film formed on said surface of said solid substrate polymerizing the polymerizable moieties (d) on said surface of said solid sub-
6. Process according to claim 5, wherein
said composition is applied to said surface of said solid substrate by coating or printing
and/or
said solid substrate comprises one or more materials selected from the group consisting of glasses, transparent conducting oxides, metals and organic polymers
and/or
said constituents (b) and (c) are removed by exposing the wet film formed on said surface of said solid substrate to air having a temperature in the range of from 20 °C to 120 °C
and/or
polymerization of said polymerizable moieties is initiated by irradiation in the presence of an initiator (e) which decomposes into radicals when exposed to said irradiation.
7. Process according to claim 5,
said process further comprising disposing a separator layer on the surface of said composite layer facing away from the solid substrate.
8. Process according to claim 5, comprising the steps of
preparing
a first layer assembly comprising a first solid substrate having a surface and arranged on said surface of said first solid substrate a composite layer as defined in claim 5, and optionally a separator layer disposed on a surface of said composite layer facing away from said first solid substrate, and
a second layer assembly comprising a second solid substrate having a surface and arranged on said surface of said second solid substrate a counter electrode layer, and optionally a separator layer disposed on a surface of said counter electrode layer facing away from said second solid substrate,
with the proviso that at least one of said first and second layer assembly comprises a separator layer
stacking and bonding said layer assemblies so that an article is obtained having a separator layer sandwiched between said first electrochromic composite layer and said counter electrode layer.
Process according to claim 7 or 8, wherein disposing said separator layer on the surface of said composite layer facing away from said first solid substrate and/or on the surface of said counter electrode layer facing away from said second solid substrate comprises the steps of
forming on said surface of said composite layer resp. said counter electrode layer a wet film by applying to said surface a composition comprising
(c") optionally a carrier liquid having a boiling point below 120 °C
(d") one or more kinds of polymerizable moieties,
(e") optionally one or more initiators for initiating radical polymerization of said one or more kinds of polymerizable moieties
(g") an aprotic organic liquid having a boiling point of 120 °C or higher
(h") optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+
in case the composition contains a carrier liquid (c") removing said carrier liquid (c") from the wet film formed on the surface of said composite layer resp. said counter electrode layer
polymerizing the polymerizable moieties in the layer formed on the surface of said composite layer resp. said counter electrode layer.
Process according to claim 9, wherein at least one of
said composition according to any of claims 1 to 4 which is applied to said surface of said first solid substrate
and said composition defined in claim 9
contains an electrolyte (h) resp. (h").
1 1. Process according to claim 8, wherein at least one of said solid substrates has a light transmission of 80 % or more measured according to DIN EN 410.
12. Process according to claim 8, wherein said counter electrode layer is obtained by depositing an electroactive material on the surface of said second solid substrate by means of sputtering.
13. Process according to claim 8 or 12, wherein said counter electrode layer comprises one or more oxides of nickel.
14. Process according to claims 8, said process further comprising attaching a first support layer to the surface of the first solid substrate facing away from said composite layer and/or attaching a second support layer to the surface of the second solid substrate facing away from said counter electrode layer, and optionally attaching a third support layer to the surface of the first support layer facing away from the first solid substrate and/or a fourth support layer to the surface of the second support layer facing away from the second solid substrate.
15. Use of a composition according to any of claims 1 to 4 for preparing a composite layer comprising
a matrix formed of one or more kinds of organic polymers
and dispersed within said matrix
(a) nanoobjects comprising one or more oxides of tungsten
(g) an aprotic organic liquid having a boiling point of 120 °C or higher
(h) optionally at least one electrolyte having cations selected from the group consisting of H+, Li+, Na+ and K+ dissolved in said aprotic organic liquid (g)
on a surface of a solid substrate.
PCT/EP2018/071480 2017-08-09 2018-08-08 Compositions comprising dispersed nanoparticles of electrochromic oxide WO2019030269A1 (en)

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