WO2005026827A2 - Durable electrooptic devices comprising ionic liquids - Google Patents

Durable electrooptic devices comprising ionic liquids Download PDF

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Publication number
WO2005026827A2
WO2005026827A2 PCT/US2004/027909 US2004027909W WO2005026827A2 WO 2005026827 A2 WO2005026827 A2 WO 2005026827A2 US 2004027909 W US2004027909 W US 2004027909W WO 2005026827 A2 WO2005026827 A2 WO 2005026827A2
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WO
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Prior art keywords
substrate
electrochromic
ionic liquid
bis
imide
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PCT/US2004/027909
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English (en)
French (fr)
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WO2005026827A3 (en
Inventor
Benjamin P. Warner
Anoop Agrawal
John P. Cronin
Juan C. L. Tonazzi
Mark T. Mccleslkey
Anthony K. Burrell
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The Regents Of The University Of California
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Priority to EP04782396A priority Critical patent/EP1702236A4/en
Publication of WO2005026827A2 publication Critical patent/WO2005026827A2/en
Publication of WO2005026827A3 publication Critical patent/WO2005026827A3/en

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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
    • 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
    • C09K9/02—Organic tenebrescent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R1/00—Optical viewing arrangements; Real-time viewing arrangements for drivers or passengers using optical image capturing systems, e.g. cameras or video systems specially adapted for use in or on vehicles
    • B60R1/02—Rear-view mirror arrangements
    • B60R1/08—Rear-view mirror arrangements involving special optical features, e.g. avoiding blind spots, e.g. convex mirrors; Side-by-side associations of rear-view and other mirrors
    • B60R1/083—Anti-glare mirrors, e.g. "day-night" mirrors
    • B60R1/088—Anti-glare mirrors, e.g. "day-night" mirrors using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials

Definitions

  • Electrooptic devices are devices in which an applied electrical voltage produces a change in the optical properties of the device. Electrooptic devices are used for many applications such as variable transmission windows used for management of solar heat gain in buildings and variable transmission automotive mirrors. A specific type of an electrooptic device is an electrochromic device, i.e. a device that changes color in response to an applied voltage.
  • Electrochromic (EC) devices are a subset of electrooptic devices, provide reversible modulation of light, and are useful for several applications. Some of the applications are rearview mirrors for automobiles, trucks, buses, scooters and motorcycles; windows for automobiles, other transportation (including road, rail, water and air) and buildings; eyewear; and attenuation or modulation of artificial lighting, displays, and contrast enhancement filters (including variable transmission filters for helmet mounted displays).
  • the only successful commercial application thus far has been for automotive rearview mirrors. High cost and lack of durability have limited commercial window applications of these EC devices.
  • the durability limitation of the EC devices arises in part due to the electrolytes and solvents used in the prior art.
  • the typical high dielectric solvents used in present day devices may have one or more of the following drawbacks: high volatility, high moisture sensitivity, hydrophilicity, a narrow range of electrochemical stability, chemical reactivity, and susceptibility to light-induced degradation (typically from ultraviolet or UV light).
  • ionic liquids that are organic solvents that are composed of ammonium cations and trifluoromethylsulfonyl- containing anions.
  • these solvents have a low flammability, thus making products incorporating them safer than products incorporating more conventional organic solvents.
  • an object of the present invention is to provide a relatively inexpensive, durable electrooptic device. Another object of the present invention is to provide electrolyte solutions for electrooptic devices. Yet another object of the present invention is to provide soluble dye compounds for use with ionic liquids for electrooptic devices. Still another object of the present invention is to provide an electrooptic device with low leakage current. Another object of the present invention is to provide an electrooptic device that utilizes low conductivity transparent conductors. Yet another object of the present invention is to provide an electrooptic device suitable for use as a rear- view mirror for vehicles such as automobiles, trucks, buses, scooters, and motorcycles.
  • Still another object of the present invention is to provide electrooptic devices having fast kinetics to color and bleach.
  • Another object of the present invention is a method of providing removing impurities, especially colored impurities, from ionic liquid precursors.
  • Still another object of the present invention is a method for preparing ionic liquid using the conjugate acid of the anion of the ionic liquid.
  • the present invention includes an electrochromic device suitable for use as a rear- view mirror.
  • the device includes a first substrate having a first surface coated with a transparent conductor, and a second substrate having a second surface coated with a second transparent conductor.
  • the second substrate is positioned in a substantially parallel relationship with the first substrate and spaced apart from the second substrate by a distance of less than about 250 microns.
  • the first surface faces the second surface.
  • the device also includes an electrochromic medium disposed between the first substrate and the second substrate; the transmission of light through the electrochromic medium changes when an electric potential is applied to the electrochiOmic medium.
  • the resistivity of at least one of the transparent conductors is greater than 20 ohms/square, and the device has a coloring speed and a bleaching speed of less than 60 seconds at temperature of from about 23 degrees Celsius to about 27 degrees Celsius.
  • the electrochromic medium includes at least one bridged dye having at least one anodic moiety and one cathodic moiety.
  • the invention also includes an electrochromic device suitable for use as an rear- view mirror.
  • the device includes a first substrate having a first transparent conductor coated surface, a second substrate having a second conductor coated surface, and a single compartment electrochromic medium disposed between the first substrate and the second substrate.
  • the second substrate is positioned in a substantially parallel spaced apart relationship from the first substrate at a distance of less than about 250 microns.
  • the first conducting surface faces the second conductor surface.
  • the electrochromic medium includes ionic liquid having an ionic concentration of cations in excess of 1 molar, and the transmission of light through the electrochromic medium changes when an electric potential is applied to the electrochromic medium.
  • the invention also includes an electrochromic device that includes a first substrate having a transparent conductor coated surface, a second substrate having a second conductor coated surface, and an electrolyte medium disposed between the first substrate and the second substrate.
  • the device includes at least one conductive surface that includes a coating of nanostructured material.
  • An electrochromic dye is attached to the nanostructured material.
  • the electrolyte medium includes ionic liquid that includes at least one anion selected from the group consisting of trifluoromethylsulfonate (CF 3 SO 3 " ) 5 bis(trifluoromefhylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis( ⁇ erfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) N " ) and tris(trifluoromefhylsulfonyl)methide ((CF 3 SO 2 ) 3 C).
  • the second substrate is positioned in a substantially parallel spaced apart relationship from the first substrate, and the first conductor surface faces the second conductor surface.
  • the invention also includes an electrochromic device, which includes a first substrate having a transparent conductor coated surface, a second substrate having a second conductor coated surface, an electrolyte medium disposed between the first substrate and the second substrate, and at least one conductive surface that includes a coating of nanostructured material.
  • An electrochromic dye is attached to the nanostructured material.
  • the electrolyte medium includes ionic liquid having a concentration greater than 1 molar.
  • the second substrate is positioned in a substantially parallel spaced apart relationship from the first substrate, and the first conductor surface faces the second conductor surface.
  • the invention also includes a photochromic device, which includes an electrochromic electrode, a light sensitive electrode substantially parallel to and spaced apart from the electrocliromic electrode, and an electrolyte medium disposed between the electrochromic electrode and the light sensitive electrode.
  • the electrolyte medium includes ionic liquid.
  • the invention also includes an electroluminscent device, which includes a first substrate having a transparent conductor coated surface, a second substrate having a second conductor coated surface that includes semiconductor nanoparticles, and an electrolyte medium disposed between the first substrate and the second substrate.
  • the second substrate is positioned in a substantially parallel spaced apart relationship from the first substrate, and the first conductor surface faces the second conductor surface.
  • the electrolyte medium includes a soluble electroluminescent dye and ionic liquid.
  • the electrolyte medium includes at least one anion selected from the group consisting of trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromefhylsulfonyl)metl ⁇ ide ((CF 3 SO 2 ) 3 C " ).
  • the invention also includes a method for preparing ionic liquid precursor substantially free of colored impurities.
  • the method includes generating ionic liquid precursor that includes colored impurities, and exposing the impure ionic liquid precursor to decolorizing agent, thereby removing the colored impurities.
  • the purified precursor can then be used to prepare ionic liquid.
  • the invention also includes a method for preparing ionic liquid. The method includes preparing a first solution of base and the conjugate acid of the anion of the ionic liquid, preparing a second solution of base and quaternary arnmonium halide, and combining the first solution with the second solution.
  • FIGURE la shows a cutaway, edge-on view of an embodiment of an electrochromic device of the invention.
  • FIGURE lb shows a perspective view of the embodiment of the electrochromic device of FIG. la.
  • FIGURE 2 shows a cutaway, edge-on view of an embodiment of an electrochromic device of the invention that includes an electrocliemically active coating.
  • FIGURE 3 shows a cutaway, edge-on view of an embodiment of an electrochromic device of the invention that includes an electrocliemically active coating and an ion- selective transport layer.
  • FIGURE 4 shows a cutaway, edge-on view of an embodiment of an electrochromic device of the invention that includes two electrocliemically active coatings.
  • FIGURE 5a-c shows a schematic representation for a vacuum-backfill process.
  • FIGURE 6 shows the absorption spectra of several solvents.
  • FIGURE 7 shows the transmission spectra of an electrochromic device that includes redox dyes in the electrolyte in colored and the bleached state.
  • FIGURE 8 shows a kinetic trace of an electrochromic device containing redox dyes in the electrolyte.
  • FIGURE 9 shows transmission spectra of an electrochromic device that includes a layer of tungsten oxide in the colored state and in the bleached state.
  • FIGURE 10 shows the method for measuring the distance between the busbars of an embodiment of the present invention.
  • FIGURE 11 shows a graph of data used to determine the Tg of an ionic liquid and a solution of an ionic liquid and a non-ionic liquid.
  • FIGURE 12 shows another graph of data used to determine the Tg of an ionic liquid and a solution of an ionic liquid and a non-ionic liquid.
  • FIGURE 13 shows the absorption spectra of a charge transfer complex and of the individual components; and
  • FIGURE 14 shows a cyclic voltammogram of the charge transfer complex formed from 5,10-dihydro-5,10-dimethylphenazine andN,N'-diethylviologen bis(trifluoromethanesulfonyl)imide in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.
  • the invention relates to electrooptic devices that employ ionic liquids as electrolyte solvents.
  • Ionic liquids are molten salts that have melting points at or below room temperature.
  • the terms "ionic liquid” and "molten salt” have the same meaning.
  • the present invention relates to electrolytes and other components and constructions of EC devices using ionic liquids as solvents.
  • the present invention relates to employing ionic liquid solvents in display devices, where individual electrodes allow pictures, words, and other images to be created and controlled through EC behavior. Processing methods are disclosed for manufacturing electrooptic devices. Careful choice of ionic liquid solvents can offer several benefits, which include a wider range for electrochemical stability (greater than 4 volts (V) and in some cases greater than 6 V); high hydrophobicity; a high decomposition temperature (ionic liquids used with the invention do not boil but they decompose at temperatures higher than 150°C and more preferably higher than 200°C); a negligible vapor pressure (see, for example, C. M. Gordon in "New developments in catalysis using ionic liquids, Applied Catalysis: General A, vol. 222, (2001) pp. 101-117; and M. J. Earle in "Diels-Alder Reactions in Ionic
  • Ionic liquid solvents of tins invention do not include the mineral acids (such as sulfuric acid).
  • Ionic liquid solvents useful with the invention include salts of organic cations in combination with either organic or inorganic anions.
  • Preferred anions of the invention contain fluorine, and include trifluoromethylsulfonate ("triflate,” CF 3 SO 3 ' ), bis(trifluoromethylsulfonyl)imide (N(CF 3 SO 2 ) 2 " ), bis(perfluoroethylsulfonyl)imide
  • trifluoromethylsulfonate (“triflate,” CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide (N(CF 3 SO 2 ) 2 " ), bis(perfluoroethylsulfonyl)imide ((C 2 F 5 SO 2 ) 2 N " )), tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " )) are preferred.
  • the most preferred anion is bis(trifluoromethylsulfonyl)imide anion (N(CF 3 SO 2 ) 2 " ) because of its low cost and high hydrophobicity.
  • the bis(trifluoromethylsulfonyl)imide anion is sometimes referred to in the prior art as bis(trifluoromethanesulfonyl)amide or bis(trifluoromefhanesulfonyl)imide, and has the structural formula O _ O II ⁇ II F 3 C— S- N— S-CF 3 II II O O
  • Preferred organic cations of molten salts used with the invention include, but are not limited to, pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, and triazolium.
  • a preferred list of quaternary ammonium based ionic liquids are all those with a glass transition temperature (T g ) lower than -40°C given in Table 1 of the publication by J. Sun, M. Forsyth, and D. R.
  • ionic liquids include tetraalkylammonium cations because ionic liquids made from these cations have minimal optical absorbance in the ultraviolet portion of the spectrum, which gives molten salts based on these cations enhanced photochemical stability (see, J. Sun et al., vide supra).
  • Quaternary ammonium cations useful with the invention may be substituted with H, F, phenyl, alkyl groups with 1 to 15 carbon atoms, and other chemical substituents. Cations may even have bridged ring structures. Most preferred quaternary ammonium cations have the formula (CH 3 CH 2 ) 3 N(R , wherein Ri is alkyl having 2-10 carbons; or have the formula (CH 3 ) 2 (CH 3 CHCH 3 )N(R 2 ), wherein R 2 is alkyl having 2-10 carbons; or have the structural formula
  • R 3 is alkyl having 2-10 carbons; or have the structural formula
  • the ionic liquid solvent is N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Since EC devices can be used in a wide range of temperatures (e.g., automotive windows may be subjected to temperatures from about -40°C to 95°C or higher), the high electrochemical stability window assures that the even when the electrochemical potentials for reducing or oxidizing EC materials change with temperature, they will be within the stability window of the ionic liquid solvent. The high hydrophobicity of the ionic liquid minimizes the likelihood of water becoming part of the electrolyte and generating electrochemical reactions that are not reversible.
  • High boiling points and low vapor pressures of ionic liquids are useful properties from the electrooptic device fabrication perspective. Most of the EC devices are backfilled in vacuum (the vacuum backfill process is described in detail later). The low vapor pressure minimizes contamination of the vacuum systems, helps keep the electrolyte composition constant, and prevents entrapment of bubbles during the backfilling process. These properties also contribute to chemical safety in the workplace. Low flammability is important from a safety perspective, particularly when used in buildings and in transportation.
  • Preferred ionic liquid solvents used with the present invention do not significantly absorb ultraviolet radiation having a wavelength above 290 nanometers (nm), and therefore do not degrade when exposed to these wavelengths to byproducts that can lead to irreversible coloration, gas formation and/or formation of electrocliemically active/inactive species.
  • the preferred ionic liquid solvents are those that can result in formulations with a Tg below 0°C, preferably below minus 20 degrees Celsius (-20°C) and most preferably below - 0°C. As will be shown in EXAMPLE 7 (vide infra), Tg can be measured from viscosity data. To make EC devices of practical use, several ingredients may be required in the electrolyte.
  • EC devices may require UV stabilizers, other co-solvents (propylene carbonate, methyl sulfolane, for example) and salts, redox dyes, viscosity modifiers, gelling materials, dyes that impart permanent colors, including those that absorb in the near infra-red region (wavelengths between 700 and 2500 nm) and opacif ⁇ ers.
  • FIGURE la shows an edge-on view
  • FIGURE lb shows a perspective view, of an embodiment of an electrochromic device of the invention.
  • Devices of this configuration are referred to as single compartment devices in the art because the electrochemical activity takes place in a single layer of material (i.e. the electrolyte) between the conductive electrodes.
  • FIGURE la-b shows electrochromic device 10, which includes first substrate 12 and second substrate 14 in a substantially parallel relationship with, and spaced apart from, first substrate 12. For convenience, small flat pieces of glass may be employed as substrates.
  • Electrochromic device 10 includes first conductive layer 16 on first substrate 12 and second conductive layer 18 on second substrate 14.
  • Conductive layers 16 and 18 are typically indium tin oxide, or fluorine-doped indium tin oxide, but any conductive coating, such as thin layers of metal or conducting polymers may be used.
  • Conductive layer 18 is needed if second substrate 14 is not conductive, for example if second substrate 14 is made of glass or plastic. However, conductive layer 18 is optional if second substrate 14 already is conductive, for example if second substrate 14 is made of metal or metal-coated glass or metal coated plastic. When second substrate 14 is conductive, then second substrate 14 functions as a structural substrate, reflector and conductive layer.
  • Electrochromic device 10 includes metallic bus bars 20, one attached to an end portion of first conductive layer 16 and another attached to an end portion of second conductive layer 18.
  • Electrochromic device 10 includes electrically non-conductive gasket 24, which forms a seal with first conductive layer 16 and with second conductive layer 18 or with second substrate 14 if second conductive layer 18 is not used to provide chamber 26.
  • the width of chamber 26, which is the width between first conductive layer 16 and second conductive layer 18, is from about 20 microns to about 5000 microns. More preferably, the chamber width is from about 40 microns to about 500 microns. Most preferably, the chamber width is less than about 250 microns.
  • Gasket 24 should be chemically stable to molten salt electrolyte used with the invention, substantially impermeable to water and the atmosphere (especially to oxygen and carbon dioxide), and robust over a wide temperature range, preferably from temperatures of about -40°C to about 100°C. Gasket 24 provides electrical insulation between the two conducting surfaces so that substantially all electrical current passes through electrolyte solution 30. Typically, the thickness of gasket 24 determines the distance between first conductive layer 16 (i.e.
  • Device 10 includes at least one port 28 for filling chamber 26 with electrolyte solution 30.
  • Port 28 may be located at any convenient location (through gasket 24, through first substrate 12, through second substrate 14, for example). Only one port is needed if vacuum-backfill techniques are used to fill chamber 26 with solution 30, but additional ports (for the purpose of, for example, pressure relief) may be present if other fill methods are used. After filling chamber 26, port(s) 28 are plugged.
  • Electrolyte solution 30 is non- volatile and hydrophobic, and provides high concentrations of cations and anions that offer minimal resistance to current.
  • Electrolyte solution 30 in chamber 26 remains in electrical contact with first conductive layer 16 and second conductive layer 18 (or with second substrate 14 if second conductive layer 18 is not used).
  • the bulk of electrolyte solution 30 is ionic liquid solvent.
  • Electrolyte solution 30 also includes at least one anodic and at least one cathodic material.
  • the anodic material and/or cathodic material may be ionic in order to improve their solubility in the ionic liquid solvent, and their associated anions are preferably identical to those of the ionic liquid solvent.
  • the anodic material and cathodic material may each be a moiety of a single bifunctional redox compound. It should be understood that the substrates are not limited to any particular shape or to any particular material.
  • Curved substrates may be used. Materials such as glass, metal, plastic, and the like may be used.
  • a substrate for a mirror application may include an opaque reflective material such as metal or metal-coated-coated plastic or metal-coated glass. If metals are used, preferred metals may include aluminum, aluminum alloys, silver, chromium, rhodium, stainless steel, and silver alloys in which the silver is alloyed with gold, palladium, platinum, or rhodium.
  • a reflective substrate may also be composed of multiple layers where some of these layers may be transparent conducting oxides to prevent reactions with electrolyte. Metals may also serve as reflectors.
  • the metals may be in contact with the electrolyte or they may be on the outside of the device. In the latter case both substrates facing inwards have coatings of transparent conductors, and the outside reflector may be the ones described above and may be further protected by copper layer and polymeric paint against corrosion.
  • a back reaction is concurrently set up in the device. This back reaction may lead to leakage current. This leakage current may be responsible for the devices to self-bleach when the coloring potential is removed. Although the back reaction is useful, too much of it leads one to use high conductivity conductive layers 16 and 18. When these conductive layers are transparent, they add cost to the device, particularly if they are low in electrical resistivity.
  • transparent conductive layers used for commercial mirrors typically have an electrical resistivity of less than 15 ohms/square. In order to keep the cost low, a preferred range being higher than 20 ohms/square and even more preferred being higher than 40 ohms/square; greater than 50 ohms/square is most preferred.
  • high resistivity (low conductivity) conductive layers are used in the same device, the high leakage current causes an iris effect, i.e., the voltage drop in this conductive layer does not allow the center of the device to color less as compared to the perimeter of the device.
  • the viscosity change causes a slower diffusion of the dye through the electrolytic medium.
  • the addition of these additives can have some drawbacks.
  • the viscosity-modifying additives may change the viscosity to a point where it becomes difficult to backfill even at elevated temperature.
  • the additives may also cause other problems such as poor UV or cyclic stability.
  • Another way to decrease the leakage current is to increase the electrolyte thickness. In this case, the dye molecules have long path lengths for diffusion.
  • time to color is the length of time required to color for 80% of the full range measured from the highest transmittance or reflectivity
  • time to bleach is the length of time required to bleach for 80% of the full range measured from the lowest transmittance or reflectivity
  • the full range is the difference between the bleached state transmittance or reflectance and the colored state transmittance or reflectance, respectively, at a specified coloring potential.
  • EC devices have a variable transmittance (or reflectance), which may be changed by coloring potential.
  • a step potential is used at the maximum safe voltage and for bleaching, and the electrodes of the device may be left open or shorted or a reverse potential may be applied.
  • the reflectivity is measured at 550 nm, or a broader wavelength measurement is made using white light that is modulated using a photopic filter.
  • a preferred way to reduce the back reaction is to use a high concentration of ionic species in the electrolyte solution.
  • a reduced back reaction results in devices that color uniformly, which is a particularly important consideration as the surface area of the electrooptic device increases.
  • the cell gap which determines the electrolyte thickness, must be less than 250 microns, more preferably less than 200 microns, and most preferably less than 150 microns in order to keep the diffusion lengths small.
  • the ionic species in the electrolyte include anions, cations, ionic liquids (i.e. molten salts), conventional salts (including inert current carrying electrolytes, lithium salts, for example) and dyes that have salt like structures (e.g., viologen salts; bifunctional dyes of this invention that include viologen moieties, and the like) and some UV stabilizers.
  • the molarity of all the ionic species added together should be greater than 1 molar, and preferably greater than 1.5 molar and most preferably greater than 2.05 molar. In commercial automotive mirrors, the ion concentration in the electrolyte is generally less than 0.1 molar.
  • the dye concentration of either the cathodic or the anodic species should preferably be less than 0.25 molar.
  • the concentration of the bridged dye should preferably be lower than 0.25 molar.
  • the dye concentrations should be lower than 0.15 molar.
  • the bifunctional dyes used with the invention provide stabilization toward ultraviolet radiation.
  • the cation of the ionic liquid solvent is preferably tetraalkylammonium, alkyl-substituted pyrrolidine, or alkyl-substituted imidazole.
  • the anion of the ionic liquid solvent is preferably perchlorate, tetrafluorborate, hexafluorophosphate, trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ).
  • the molten salt is N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.
  • Solution 30 may optionally contain thixotropic agents, such as dispersed, electrochemically inert inorganic materials such as silica or alumina to facilitate injection into chamber 26.
  • Solution 30 may also contain one or more coloring agents to afford a desired color in either a darkened state or a bleached state.
  • Solution 30 may contain additional soluble ultraviolet (UV) stabilizers, including those described in, for example, Modern Plastics World Encyclopedia (2001) p-C-120 to C- 122, Chemical Week Publishing, NY, incorporated by reference herein.
  • Solution 30 may also contain one or more stiffening agents to increase the viscosity of solution 30 while maintaining conductivity. This is desirable in order to minimize the spread of solution 30 if device 10 is damaged.
  • Stiffening agents include, but are not limited to, organic monomers and polymers such as poly(acrylonitrile), poly(vinylidene fluoride), poly(hexafluoropropylene), poly(vinylalcohol), poly(vinylacetate), poly(methylmethacrylate) and their copolymers. These polymers may also be formed by in-situ polymerization. They may be crosslinked in situ by polymerization of monomers (see, for example, U.S. Patent 6,420,036 to D. V. Varaprasad et al.
  • Poly(methylmefhylacrylate) PMMA
  • PMMA poly(methylmefhylacrylate)
  • Solution 30 optionally includes one or more soluble co-solvents that decrease the viscosity of solution 30 and do not interfere with the durability and function of the electrochromic device.
  • co-solvents are aprotic and have high boiling points (preferably above 150°C), low melting points (preferably below -30°C), and are present in concentrations from about 0.5% to about 30%.
  • co-solvents include propylene carbonate, N-mefhyl pyrrolidinone, perfluorodecalin, and perfluorodecane.
  • electrochromic device 10 may include pseudo-reference electrode 32 for evaluating the electric potential of conductive layer 16.
  • Pseudo-reference electrode 32 may be in the form of a silver wire inserted through gasket 24 such that pseudo reference electrode 32 does not contact conductive layer 16 or conductive layer 18.
  • Pseudo-reference electrodes may take other forms.
  • a minor portion of first conductive layer 16 or second conductive layer 18, for example, may be separated away by etching a separation line to provide a pseudo-reference electrode.
  • the invention may be used with a standard, glass, multiple-pane window by, for example, substituting one or more panes of a multiple glass pane window with an electrooptic device of the invention.
  • the glass panes may be coated with low-emissivity materials that block attenuate UV, infrared, and/or visible light.
  • There are many patents that describe EC devices. Some that describe EC devices utilizing non-ionic liquid electrolytes include U. S. Patent 4,902,108 to H. J.
  • Electrochromic Medium which issued on August 17, 1999, all incorporated by reference herein.
  • plasticizing the polymers with the liquid electrolytes produces solid electrolytes.
  • the solvents described in these patents are neutral polar materials such as nitriles (e.g., glutaronitrile, 3-hydroxypropionitrile), sulfolanes (e.g., 3-methylsulfolane), ethers (e.g., polyethylene oxide, polypropyleneoxide and tetraglyme), alcohols
  • UV stabilizers include materials that absorb UV (ultraviolet) radiation and materials that quench species generated by the UV radiation to minimize damage caused by UV radiation. Any UV stabilizer or any of the other ingredients, including dyes, must be soluble in the electrolyte within the temperature ranges in which the device is used. For electrochromic mirrors, windows and other devices that are subjected to the weathering elements, UV stabilizers must be compatible over a wide temperature range.
  • a preferred minimum temperature range for devices to operate is from 0°C to 50°C, a more preferred range is from -20°C to 70°C, and a most preferred range is from -40°C to 105°C.
  • UV stabilizers that can be used with the invention can be found in Modern Plastics Encyclopedia, pages C 120 to C122, 2001, Chemical Week Associates publication, New York, incorporated by reference herein. Some of the preferred UV stabilizers are benzophenone and derivatives thereof because these materials are compatible with several ionic liquids (see M. Muldoon et al. in "Hydrogen abstraction from ionic liquids by benzophenone triplet excited states," Chem. Comm. (2001) p. 2364- 2365; D.
  • UV stabilizers are benzotriazoles (and derivatives thereof) and triazines (and derivatives thereof). The addition of UV stabilizers can also assist in decreasing the freezing point of the electrolytes, as they may constitute 0.01% to 40% of the weight of the molten salt solution.
  • UV stabilizers typically result in an average absorbance of greater than 1.00 between the wavelengths of 290 nm and 400 nm (90% of attenuation of UV) and more preferably in an absorbance greater than 2.00 (99% attenuation of UV), as measured with a path length of one centimeter and a concentration of about 1% by weight of the UV stabilizer in the ionic liquid. This absorbance is measured by subtracting the absorbance of the ionic liquid without the UV stabilizer from the absorbance of the solution that contains the UV stabilizer.
  • bifunctional redox dyes that have tethered UV stabilizer moieties is that the UV stability of the entire device is increased. Additional examples of bifunctional redox dyes having a dye moiety attached to a UV stabilizer moiety are described in U. S. Patent 6,362,914 to K. Baumann et al., entitled “Electrochromic Materials with Enhanced Ultraviolet Stability and Devices Comprising the Same," which issued March 26, 2002, incorporated by reference herein.
  • the '914 patent describes a cathodic compound prepared by attachment of a viologen dye to an UV stabilizer moiety, which is referred to in the '914 patent as an "energy receptor site".
  • UV stabilizer moieties include benzophenones or benzotriazoles, which can be covalently attached to either an anodic or cathodic dye moiety.
  • the UV stabilizer moiety of the compound absorbs the UV radiation and prevents damage to the dye moiety.
  • a specific example of such a compound described in the '914 patent is 1 -methyl- 1-[1- benzotriazole-2-hydroxy-3-t-butyl-5-propyl(propionate)-[benzene]]-4,4-bipyridinium bis(tetrafluoroborate).
  • a different compound is employed, one in which at least one tetrafluoroborate and preferably both tetrafluoroborate anions are replaced with trifluoromethylsulfonate
  • a compound containing bis(trifluoromethylsulfonyl)imide may be prepared by anion exchange of the corresponding tetrafluoroborate anion-based compound with bis(trifluoromethylsulfonyl)imide anion.
  • this type of compound may be synthesized by the electrochemical oxidation of the anodic moiety (e.g.
  • a phenazine moiety in an ionic liquid that includes bis(trifluoromethylsulfonyl)imide anions, or by the electrochemical reduction and re-oxidation of the cationic moiety (e.g. a viologen moiety) in the same ionic liquid.
  • the cationic moiety e.g. a viologen moiety
  • cathodic moieties of bifunctional redox dyes of the present invention include those defined by the following structural formulae:
  • R 5 is independently selected from alkyl Ci to C 20 , alkynyl C 2 to C 20 , and aryl C 5 to C 20 .
  • R 5 may optionally contain one or more of an ester, carboxylic acid, metal carboxylate, ether, aryl, amine, urethane, ammonium, thioester, alkene, and alkyne functional group, and additionally may function as a bridge to an energy receptor moiety.
  • R is independently selected from hydrogen, alkyl C ⁇ to C 10 , alkynyl C 2 to C 10 , aryl C 5 to C 20 , and may optionally contain one or more of an ester, carboxylic acid, metal carboxylate, ether, aryl, amine, urethane, ammonium, thioester, alkene, and alkyne functional groups, and additionally may function as a bridge to an energy receptor moiety.
  • Anion A " is a trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N ⁇ ), bis(perfluoroethylsulfonyl)imide
  • anion B " is a halogen anion, ClO 4 " , BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , CH 3 COO “ , CH 3 (C 6 H 4 )SO 3 " , trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N “ ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO2)2N “ ) or tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C “ ) anion.
  • Energy receptor moieties include those having the following chemical structures:
  • R 7 is independently selected from alkyl Ci to C 0 , alkynyl C 2 to C 20 , and aryl C 5 to C 2 o, and may optionally contain one or more of an ester, carboxylic acid, metal carboxylate, ether, aryl, amine, urethane, ammonium, thioester, alkene, and alkyne functional group, and additionally may function as a bridge to the energy receptor moiety.
  • Any of the above cathodic moieties when suitably bridged to any of the energy receptor moieties forms a bifunctional redox dye, and all of these compounds are examples of bifunctional redox dyes of the invention.
  • Examples of anodic moieties of bifunctional redox dyes of the present invention include those defined by the following structural formulae:
  • R 8 is independently selected from alkyl Ci to C 20 , alkynyl C 2 to C 20 , and aryl C 5 to C 20 and may optionally contain one or more of an ester, carboxylic acid, metal carboxylate, ether, aryl, amine, urethane, ammonium, thioester, alkene, and alkyne functional group, etc, and additionally may function as a bridge to an energy receptor moiety.
  • the energy receptor moiety is one having the structure
  • bifunctional redox dyes of the invention when they are oxidized in ionic liquid solvent, a radical cation is formed that is charge counterbalanced with the anion from the ionic liquid solvent.
  • An important aspect of the invention is that the bifunctional redox dyes of the invention are soluble in the preferred ionic liquid solvents of the invention in their oxidized, reduced and intermediate states. These dyes are reduced and/or oxidized in the device when the voltage is applied. This oxidation or reduction is reversible. Furthermore, one or more of the oxidized or reduced species should be different in color as compared to its earlier state (before application of the voltage).
  • a bifunctional redox dye may include in a single molecule, both an anodic moiety and a cathodic moiety, and this type of dye may undergo both oxidation and reduction at the two electrodes.
  • Preferred cathodic moieties of the bifunctional dyes of the invention include viologens, which are cationic.
  • viologens are N,N'-diethylviologen ("ethyl viologen”), N,N' -dimethyl viologen (“methyl viologen”) and N,N'-dibenzylviologen (“benzyl viologen”) associated with fluorine containing anions such as BF “ , PF 6 " , AsF 6 “ , SbF 6 " , trifluoromethylsulfonate (CF3SO3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis( ⁇ erfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C).
  • ethyl viologen N,N' -dimethyl viologen
  • benzyl viologen N,N'-dibenzyl
  • Preferred anions are trifluoromethylsulfonate (CF 3 SO3 " ), bis(trifluoromethylsulfonyl)imide ((CF3SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF3S ⁇ 2)3C " ).
  • Preferred anodic moieties of the bifunctional dyes of the present invention include metallocenes (particularly ferrocenes), phenazines, phenothiazines, fulvalenes, and substituted 1,4- or 1,2-phenylenediamines, including their derivatives and combinations.
  • Some preferred phenazines are 5,10-dihydro-5,10-dimethylphenazine; 5,10-dihydro-5,10- diethylphenazine; 5,10-dihydro-5,10-dioctylphenazine or any other 5,10-dihydro-5,10- dialkyphenazine.
  • Preferred phenylenediamines include TMPD (N,N,N',N'- tetramethylphenyldiamine) and TMBZ (N,N,N',N'-tetramethylbenzydine).
  • a preferred fulvalene is tetrathiafulvalene.
  • Preferred ferrocenes of the invention include electron-donating groups that are attached to one or both of the cyclopentadiene rings, such as tertiarybutylferrocene and decamethylferrocene. Some of these anodic dyes may have to be fluorinated to increase their solubility in specific ionic solvents.
  • the concentration of any of the dyes is less than 0.1 molar, preferably less than 0.05 molar.
  • At least one of the cathodic or anodic moieties of the bifunctional redox dye must be electrochromic in the reduced or the oxidized state with an absorption in the visible region of the electromagnetic radiation. As the dye moiety reversibly goes back to its non- activated form, the absorption should also reverse, meaning either shift or decrease to its earlier state.
  • Two or more separate dye compounds are often used with electrochromic devices to control the device properties such as the color of the device, the kinetics, etc. (see, for example, U. S. Patent 6,141,137 to H. J. Byker et al.
  • Patent 6,241,916 to U. Claussen et al., entitled “Electrochromic system,” which issued June 5, 2001, and in PCT application WO 01/163350 to Lomprey et al. (vide supra), all incorporated by reference herein.
  • the 6,519,072 and 6,241,916 patents describe dyes where the anodic and the cathodic dyes are not separate molecules, but instead, each is present as either an anodic moiety or a cathodic moiety, and connected in the same molecule.
  • the cyclic voltammogram of such a molecule displays at least one reduction peak and at least one oxidation peak that are derived from the compound when measured from the resting state (i.e. when there is no applied electrochemical potential).
  • Either the reduction or oxidation process, and preferably both the reduction and oxidation processes, are accompanied by an increase in the molar extinction coefficient at at least one wavelength in the visible range.
  • the present invention includes bifunctional redox dyes having a cathodic moiety covalently bridged to an anodic moiety. These compounds often have good UV stability.
  • An example of such a UV stable dye is produced when a ferrocene moiety is coupled with a viologen moiety using an appropriate linker or bridge, and it was shown that a material of this type provides both anodic and cathodic redox in the electrolytes for electrochromic devices using conventional non-ionic solvents.
  • Bifunctional redox dyes having anodic and cathodic moieties may be bridged with energy receptor moiety display to increase their UV stability even more.
  • These types of dyes, when used with ionic liquid solvents according to the present invention are expected to provide electrooptic devices that would be most suitable for outside environment use, both in colored and bleached states.
  • the present invention includes bifunctional compounds having both anodic and cathodic moieties, wherein one or more are cationic moieties in the resting state, oxidized state, or reduced state, and are charge balanced by trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 S O 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 )2N ⁇ ) and/or tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ), preferably by bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ).
  • These compounds may be synthesized by anion exchange, for example, by reacting the salts described in U.S. Patent 6,519,072 (vide supra) with lithium bis(trifluoromefhylsulfonyl)imide (Li(CF 3 SO 2 ) 2 N ⁇ ) in water.
  • compounds in which some of the cationic charges are balanced with bis(trifluoromethylsulfonyl)imide anions may be synthesized by the electrochemical oxidation of the anodic moiety (e.g. a ferrocene moiety) in an ionic liquid solvent that includes bis(trifluoromethylsulfonyl)imide anions.
  • Compounds in which some of the cationic charges are balanced with bis(trifluoromethylsulfonyl)imide anions may also be synthesized by the electrochemical reduction and re-oxidation of the cationic moiety (e.g. a viologen moiety) in an ionic liquid that includes bis(trifluoromethylsulfonyl)imide anions.
  • the present invention also includes the use of these compounds in an electrooptic device.
  • the cathodic moiety of bifunctional dyes of the invention includes viologens (which have a bipyridinium ion-pair structures) or anthraquinones, while the anodic moiety has a pyrazoline, metallocene, phenylenediamine, benzidine, phenazine, phenoxadine, phenothiazine, or tetrathiafulvalene structure, or is a metal salt that can be oxidized in the ionic liquid solvent.
  • Electrochromic compounds in which the anodic and cathodic moieties are present in the same molecule, and including at least one anion that is the same as the anion of the ionic liquid solvent preferably include viologens with a bipyridinium ion-pair structure represented by the structural formula
  • a " is selected from trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ), and B " is selected from halogen anion, CIO 4 -, BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , CH3COO " , and CH 3 (C 6 H 4 )SO 3 -, trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethyl
  • R 10 and R ⁇ are each independently a hydrocarbon group selected from alkyl, alkenyl and aryl groups having 1 to 10 carbon atoms.
  • R 10 or R ⁇ is an aryl group
  • the aryl group may form a condensed ring together with a cyclopentadienyl ring.
  • alkyl group examples are methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl groups.
  • the aryl group is exemplified by the phenyl group. Particularly preferred are methyl, ethyl, and propyl groups.
  • R 10 or R ⁇ is an aryl group
  • the aryl group may form a condensed ring by bonding to a cyclopentadienyl ring, and R 10 or R ⁇ may be a group cross-linking two cyclopentadienyl rings in the metallocene structure.
  • m and n are preferably 0 or 1, and particularly preferably 0.
  • Me is preferably Fe.
  • Preferred electrochromic compounds in which the anodic and cathodic moieties are present in the same molecule, and including at least one cationic moiety, are metallocene- bipyridine derivatives represented by the following formulae:
  • a " is selected from trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C ' ), and B " is selected from halogen anion, ClO 4 " , BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , CH 3 COO “ , CH 3 (C 6 H 4 )SO 3 “ , trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3
  • Rio and Ri t are each independently a hydrocarbon group selected ftom an alkyl group, alkenyl group, or aryl group having 1 to 10 carbon atoms.
  • R 10 or R ⁇ is an aryl group
  • the aryl group may form a condensed ring together with a cyclopentadienyl ring.
  • R 12 and R 13 are each independently a hydrocarbon residue having 1 to 20, preferably 1 to 10 carbon atoms
  • R 14 is a hydrocarbon group selected ftom alkyl, cycloalkyl, alkenyl, aryl, or aralkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and a substituted hydrocarbon or heterocyclic group obtained by substituting one or more hydrogen atoms of the hydrocarbon group or heterocyclic group with a substituent group.
  • Me represents Cr, Co, Fe, Mn, Ni, Os, Ru, V, Mo(X)(Q), Nb(X)(Q), Ti(X)(Q), V(X)(Q) or Zr(X)(Q) wherein X and Q are each independently selected from hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, ClO 4 " , BF 4 ' , PF 6 " , AsF 6 “ , SbF 6 “ , CH 3 COO " , and CH 3 (C 6 H 4 )SO 3 " , trifluoromethylsulfonate (CF3SO3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF3SO 2 ) 3 C
  • hydrocarbon residue for R 12 and R 13 examples are hydrocarbon groups such as alkylene groups and various divalent groups having an ester-bond unit, ether-bond unit, amide-bond unit, thioether-bond unit, amine-bond unit, urethane-bond unit, or silyl unit in the part of hydrocarbon groups.
  • the divalent group having an ester-bond unit may be exemplified by those represented by the formula -R-COO-R- or -R-OCO-R- wherein R is an alkylene group having 1 to 8 carbon atoms.
  • ester-bond unit examples include -C 4 H 8 -COO-C 2 H 4 , -C 4 H 8 -OCO-C 2 H 4 -, -C 4 H 8 -COO-C 4 H 8 -, and -C 4 H 8 -OCO-C 4 H 8 -.
  • the divalent group having an ether-bond unit may be exemplified by those represented by the formula -R-O-R- wherein R is an alkylene group having 1 to 10 carbon atoms.
  • the ether-bond unit are -C 4 H 8 -O-C 2 H 4 - and -C 4 H 8 -O-C 4 H 8 -.
  • the divalent group having an amide-bond unit may be exemplified by those represented by the formula -R-CONH-R- or -R-NHCO-R- wherein R is an alkylene group having 1 to 8 carbon atoms.
  • Specific examples of the amide-bond unit are -C 4 H 8 -CONH-C 2 H 4 -, -C 4 H 8 -NHCO-C 2 H 4 -, -C 4 H 8 - CONH-C 4 H 8 -, and -C H 8 -NHCO-C 4 H 8 -.
  • the divalent group having a thioether-bond unit may be those represented by the formula -R-S-R-wherein R is an alkylene group having 1 to 10 carbon atoms.
  • R is an alkylene group having 1 to 10 carbon atoms.
  • Specific examples of the thioether-bond unit are -C H 8 -S-C 2 H - and - C 4 H 8 -S-C 4 H 8 -.
  • the divalent group having an amine-bond unit may be exemplified by those represented by the formula -R-NH-R- wherein R is an alkylene group having 1 to 10 carbon atoms and the formula -R-NH-Ph- wherein R is an alkylene group having 1 to 10 carbon atoms and Ph is an arylene group or a substituted arylene group having 1 to 12 carbon atoms.
  • Specific examples of the amine-bond unit are -C 4 H -NH-C 2 H 4 - and -C H 8 -NH-C H 8 -.
  • the divalent group having a urethane-bond unit may be exemplified by those represented by the formula -R-OCONH-R- or -R-NHCOO-R- wherein R is an alkylene group having 1 to 8 carbon atoms.
  • R is an alkylene group having 1 to 8 carbon atoms.
  • Specific examples of the urethane-bond unit are -C 4 H 8 -OCONH-C 2 H -, -C 4 H 8 -NHCOO-C 4 H 8 -, -C 4 H 8 -OCONH-C 4 H 8 -, and -C 4 H 8 -NHCOO-C 4 H 8 -.
  • the divalent groups having a silyl-bond unit may be represented by those represented by the formula -R-Si(R') 2 -R- wherein R is an alkylene group having 1 to 8 carbon atoms and R' is methyl or ethyl.
  • R is an alkylene group having 1 to 8 carbon atoms and R' is methyl or ethyl.
  • Specific examples of the silyl-bond unit are - C 4 H 8 -Si(CH 3 ) 2- C 2 H 4 -, -C 4 H 8 -Si(CH 3 ) 2 -C 4 H 8 -, -C 4 H 8 -Si(C 2 H 5 ) 2- C 2 H 4 -, and -C 4 H 8 - Si(C 2 H 5 ) 2 -C 4 H 8 -.
  • Examples of the alkyl group for R 14 are methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, and n-heptyl groups.
  • An example of the cycloalkyl group is cyclohexyl.
  • Examples of the aryl group are phenyl, tolyl, xylyl, and naphthyl.
  • Examples of the alkenyl group are vinyl and allyl groups.
  • Examples of the aralkyl group are benzyl and phenylpropyl groups.
  • heterocyclic aromatic group examples include 2- pyridyl, 4-pyridyl, 2-pyrimidyl, and isoquinoline groups.
  • substituents examples include alkoxy, alkoxycarbonyl, and acyl group having 1 to 10, preferably 1 to 5 carbon atoms, halogen, and cyano (-CN group), hydroxyl, nitro, and amino groups.
  • alkoxy group examples include methoxy and ethoxy groups.
  • the alkoxycarbonyl group is exemplified by methoxycarbonyl.
  • the acyl group is exemplified by acetyl.
  • halogen group examples include CI and F.
  • substituted hydrocarbon residue examples include methoxyphenyl, chlorophenyl, fluorophenyl, methoxychlorophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, and methoxynapthyl groups.
  • metallocene-bipyridine bifunctional redox dyes of the invention may be synthesized by first synthesizing a precursor as described in U.S. Patent 6,519,072 (vide supra) and then exchanging some or all of the anions by, for example, suspending or dissolving the precursor in water and combining it with an excess of lithium bis(trifluoromethylsulfonyl)imide.
  • dyes include anions such as tetrafluoroborate, perchlorate, methanesulfonate, trifluoromethanesulfonate, perfluorobutanesulfonate, benzenesulfonate, hexafluorophosphate, hexafluoroarsenate and hexafluorosilicate (SiF 6 2" ), perfluorinated main group compounds, sulfonates, and perchlorate, but none include sulfonamides or perfluorosulfonylimides.
  • anions such as tetrafluoroborate, perchlorate, methanesulfonate, trifluoromethanesulfonate, perfluorobutanesulfonate, benzenesulfonate, hexafluorophosphate, hexafluoroarsenate and hexafluorosilicate (SiF 6 2" ), perfluorinated
  • bifunctional dyes of the present invention include at least one anion selected from bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromethylsulfonyl)methide ((CF SO 2 ) 3 C " )-
  • all of the anions are bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N ⁇ ) or tris(trifluorometl ⁇ ylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ).
  • the electrochromic system according to the invention includes bifunctional dyes having the formula or having the formula Cati-Bridgei-Ani , or having the formula Cati-Bridgei-Ani-Bridge 2 -Cat2, or having the formula An2-Bridge 2 -Cat 1 -Bridge 1 -Ani, in which Catt and Cat 2 independently represent cathodic moieties, and Am and An 2 independently represent anodic moieties.
  • Bridge ! and Bridge 2 independently represent a bridge member.
  • bifunctional redox dyes include at least one anion selected from bis(trifluoromethylsulfonyl)imide ((CF3SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ).
  • the present invention also includes the radical cations of these dyes having these anions.
  • Cat ! and Cat 2 independently represent the following structural formulae:
  • Ei and E 2 independently of one another denote O, S, NR3 6 or C(R 36 )2 or Ei and E 2 together form a -N-(CH 2 ) 2 -N- bridge,
  • R 36 denotes Ci to C 18 alkyl, C 2 to C 12 alkenyl, C to C 7 cycloalkyl, C 7 to C 15 aralkyl or C 6 to Cio aryl.
  • C “ is selected from bis(trifluoromethylsulfonyl)imide ((CF 3 S O 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N “ ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ), and D ' is selected from halogen anion, ClO 4 " , BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ , CH 3 COO “ , CH 3 (C 6 H 4 )SO 3 “ , trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 S0 2 ) 2 N “ ) and tris(
  • Ani or An 2 independently represent metal salts that include titanium (III), vanadium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), tin (II), antimony (III), bismuth (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II), or europium (II).
  • R 37 to R 4 independently of one another denote Ci to C 18 alkyl, C 2 to C 12 alkenyl, C 3 to C cycloalkyl, C 7 to C 15 aralkyl or C 6 to Cio aryl, and R4 1 to R ⁇ additionally denote hydrogen.
  • R 50 independently of one another denote hydrogen, Ci to C 18 alkyl, Ci to C 18 alkoxy, halogen, cyano, nitro, Ci to C 18 alkoxycarbonyl or C 6 to Cio aryl and R 4 8 and ig additionally denote an optionally benzo-fused aromatic or quasiaromatic five- or six-membered heterocyclic ring and R 50 additionally denotes N(R 5 i))(R 52 ).
  • E 5 to E 8 independently of one another denote S, Se or NR 51 .
  • R 51 and R 5 independently of one another denote Ci to C 12 alkyl, C 2 to C 8 alkenyl, C3 to C 7 cycloalkyl, C 7 to C 15 aralkyl or C 6 to Cio aryl.
  • Bridge 2 is effected by one of the radicals R 37 - Rs , R 59 , or R 6 o and the radicals mentioned then represent a direct bond, and Bridge 1 or Bridge 2 independently represents a bridge member of the formula -(CH 2 ) n - or -(Yi)s-(CH 2 ) m -(Y 2 ) 0 -(CH 2 )p-(Y3)q-, each of which is optionally substituted by d to C 4 alkoxy, halogen or phenyl.
  • Yi to Y3 independently of one another represents O, S, NR 6 ⁇ , COO, CONH, NHCONH, cyclopentanediyl, cyclohexanediyl, phenylene, naphthylene, or beta-dicarbonyl.
  • the invention also includes the corresponding radical anions of the aforementioned cathodic compounds, the radical anions being generated in situ during electrochemical reduction, and for charge balance, necessarily include ammonium cations of the type present in the ionic liquid solvent.
  • Electrochromic compounds of the invention also include bifunctional redox dyes having a redox active cathodic moiety that provides the dye with its color properties, and a redox active metal species such as titanium (III), titanium (IV), vanadium (III), vanadium (IV), vanadium (V), iron (II), iron (III), cobalt (II), cobalt (III), copper (I), copper (II), silver (I), silver (II), indium (I), indium (III), tin (II), tin (IV), antimony (III), antimony (V), bismuth (III), bismuth (V), cerium (III), cerium (IV), samarium (II), samarium (III), dysprosium (II), dysprosium (III), ytterbium (II), ytterbium (III), europium (II), europium (III).
  • a redox active metal species such as titanium (III), titanium (IV),
  • EC devices of the present invention may also be prepared from electrolyte solutions of ionic liquid solvents, redox active cathodic dyes (viologens, for example) and a redox active metal in which the dye and metal form a bifunctional dye in the form of a metal- arene complex (metal-arene complexes are described in, for example, M. Niemeyer, "Sigma-Donor versus ⁇ - Arene Interactions in Monomeric Europium(II) and Ytterbium(II) Thiolates: An Experimental and Computational Study," Eur. J.
  • Bifunctional redox dyes of the present invention that are in the form of metal-arene complexes have the formula [Cat ⁇ ][MJ where M is a metal salt that includes a metal such as titanium (III), vanadium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), tin (II), antimony (III), bismuth (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II), or europium (II).
  • M is a metal salt that includes a metal such as titanium (III), vanadium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), tin (II), antimony (III), bismuth (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II), or
  • Charge transfer compounds include at least one electron rich aromatic compound and at least one electron deficient aromatic compound; the electron rich compound and electron deficient compound combine in ionic liquid solvent to form the charge transfer compound.
  • the UV-VIS spectrum of the charge transfer compound is not a simple linear combination of the spectra of the electron rich compound and electron deficient constituents (see FIGURE 13), and may have other properties such as enhanced solubility.
  • the spectrum of the green, charge transfer compound formed by combining 5,10-dihydro-5,10-dimethylphenazine (a white compound) with diethyl viologen bis[bis(trifluoromethylsulfonyl)imide] (another white compound) in a 1 :1 ratio includes absorption bands different ftom any present in the absorption spectra for either 5,10-dihydro-5,10-dimethylphenazine or N,N'- diethyiviologen bis[bis(trifluoromethylsulfonyl)imide] .
  • the present invention also includes electrooptic devices employing electrolyte solutions of charge transfer compounds dissolved in ionic liquids.
  • the present invention also includes charge transfer compounds having anions that are redox-inert colorless anions, where at least one anion is chosen from bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis( ⁇ erfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ).
  • at least one anion is bis(trifluoromethylsulfonyl)imide ((CFsSO ⁇ N " ).
  • anions are identical and chosen from bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N " ) and tris(trifluoromethylsulfonyl)methide ((CF 3 SO 2 ) 3 C " ).
  • the only anion is bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 )2N " ).
  • additives employed to change specific properties of the electrolyte solution of the invention. One of these is a viscosity modifier.
  • Viscosity modifiers can be soluble polymers and fillers such as fumed silica, fine alumina, etc.
  • Additives also include co-solvents, such as other ionic and non-ionic liquids. Some of these are used to change the physical properties of the electrolyte solution, such as the melting point. Additives may also change electronic properties (speed of response, current/time characteristics) of the electrolyte, and thus of electrooptic devices of the invention employing the electrolyte, by changing the viscous drag on the dyes. Some of these, which are described in U.S. Patent 5,140,455, decrease the leakage current or the back reaction.
  • ionic liquids are themselves conducting, other ionic species such as solid salts may also be added to depress their freezing points, change the ionic conductivity or provide other characteristics (e.g., ions for intercalation, etc.) as discussed later.
  • the presence of high concentrations of ionic species may suppress the bleaching reaction.
  • a mixture of a conventional solvent (i.e. a non-ionic solvent) and an ionic liquid, or a mixture of two or more ionic liquids provides electrolyte solutions with the high ionic concentrations of an ionic liquid and the low viscosity characteristic of conventional non- ionic solvents.
  • Solvent mixtures may allow viscosity control, change in ionic conductivity, change in freezing point, change in kinetics of the electrooptic reactions, change in solubility (e.g. of other added ingredients such as dyes and UV stabilizers), enhanced processability, or other characteristics.
  • Another way of measuring the concentration is by molarity, i.e. moles of ions per liter of solution.
  • the concentration of ionic species in the electrolytes of EC devices is the sum-total of all the species that are salt-like (i.e.
  • a preferred concentration of all ionic species in the electrolyte solution is greater than 1 mole/liter (molar, M) and more preferably greater than 2 M and most preferably greater than 3 M. Assuming no change in volume after mixing l-butyl-3- imidazolium bis(trifluoromethanesulfonyl)imide and propylene carbonate in a 80%/20% mixture by volume, a 2.7 M concentration of the ionic species is present.
  • the preferred concentrations of ionic species of the present invention are higher than those described in U. S. Patent Application Publication 20020021482.
  • concentrations are in the range between about 0.1 M and 1 M.
  • concentrations are in the range between about 0.1 M and 1 M.
  • ionic liquids and non-ionic cosolvent additives is a 50:50 volume mix of a preferred ionic liquid n-butyl n-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP) and propylene carbonate (PC). This mix results in a solution where the ionic concentration is 1.66 molar, assuming no change in volume occurs upon mixing the two liquids.
  • BMP n-butyl n-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide
  • PC propylene carbonate
  • the high ionic concentrations of the present invention are employed for increased durability, so that they dominate the electrolyte properties. For this, a concentration in excess of 1 molar of all ionic species is preferred, and more preferably in excess of 2 molar and most preferably in excess of 3 molar.
  • mixed ionic liquid-conventional solvent systems provide benefits such as lowered Tg, high coloration uniformity, and an acceptable leakage current (steady-state current). The leakage current of a device is measured by applying a steady voltage to hold the device in a given state of optical transmission or reflection and then measuring the current in the steady state.
  • non-ionic co-solvents used with the invention are propylene carbonate (PC), ethylene carbonate, sulfolane, methyl sulfolane, and gamma- butyrolactone.
  • PC propylene carbonate
  • ethylene carbonate ethylene carbonate
  • sulfolane sulfolane
  • methyl sulfolane sulfolane
  • gamma- butyrolactone gamma- butyrolactone
  • non-ionic solvents in the '262 patent are referred to as plasticizers, and include triglyme, tetraglyme, acetonitrile, benzylacetone, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, butylene carbonate, propylene carbonate, ethylene carbonate, glycerine carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose, gamma-butyrolactone, 2-methylglutaronitrile, N,N'- dimethylformamide, 3-methylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3,31- oxydipropionitrile, 2-methoxyethyl ether, triethylene glycol dimethyl ether, or combinations thereof.
  • Self-erasing electrochromic devices as shown in FIGURE 1 show exceptionally even coloration.
  • Devices of this construction have at least one electrochemically active material, sometimes referred to as a redox active material or redox dye, providing a redox reaction that is accompanied by a color change.
  • the devices constructed as per Figure 1 are also referred to as single compartment, as all the electrochemical activity takes place only in one compartment defined by the electrolyte layer contained within two conductors and the gasket.
  • Self-erasing refers to the spontaneous or automatic reversal of the electrooptic coloration, which occurs shortly (e.g. typically seconds to minutes, but may be longer depending on the electrolyte composition) after the activating power to the device is removed.
  • the device then returns to its non-powered state of coloration.
  • Reversion to the optical properties of the device in the non-powered state should occur quickly, e.g. in less than five minutes, and preferably in less than thirty seconds, for a electrochromic dimming mirror; these times refer to the time for bleaching and coloration to 50% of the coloration range. Desirable coloration and bleaching times depend on the use of the electrooptic device.
  • Electrochromic windows can have relatively slow coloration times and should have relatively slow bleaching times, sometimes referred to as the open circuit memory as described in A. W. Czanderna et al. in "Durability Issues and Service Lifetime Prediction of Electrochromic Windows for Buildings Applications," Solar Energy Materials and Solar Cells, vol. 56, (1999), pp.
  • Electrooptic displays such as computer displays, should have faster kinetics than electrochromic windows; signage in an electrooptic display that is occasionally updated can have slower kinetics.
  • Self-bleaching occurs because the devices have a competing back reaction in the powered state that can be measured by the leakage current in the steady state for a given coloration for a given voltage. Some back reaction is required for self-erasure, e.g. for automotive rear- view mirrors. However, high values may cause many other problems, such as uneven bleaching as described below.
  • the forward reaction e.g.
  • uniform coloration is enhanced by the high ionic concentration of the electrolyte solutions that are part of the present invention, while the back reaction, e.g. bleaching, is slowed by the viscosity of the liquid electrolytes and the concentration of the ionic species. Fast forward reactions and slow back reactions lead to more uniform voltage across the area of the device and highly uniform coloration of the electrooptic devices of the present invention.
  • the uniform coloration in the present invention is beneficial in several ways. First, uniform coloration allows larger area devices to be made; these devices color uniformly when the power is applied via the conductors, typically busbars, at the perimeter of the device.
  • the devices color deeper close to the busbar region at the perimeter then in the middle, as the size of the device increases.
  • the voltage across the device is more uniform, reducing electrophoretic segregation of the redox dyes in the activated state.
  • electrophoretic separation of the redox dyes leads to formation of colored bands near the busbars when the power is left for long periods, e.g., for tens of minutes and longer.
  • the back reaction and forward reaction usually do not uniformly increase with temperature, and in electrooptic devices using conventional non- ionic solvents the difference in rates between the forward reaction and back reaction may be so high that a uniformly coloring device at 25°C may color non-uniformly at 40°C.
  • non-uniformity tends to increase with increasing size of the device, most deleteriously with the increase in the distance between the busbar and the part of the electrodes farthest from the busbar.
  • Temperature variation particularly affects exterior automotive mirrors, which are typically larger than the interior mirrors and may be heated to remove frost in cold weather or they may require coloration during the day to increase safety to be able to reduce solar glare.
  • FIGURE 10 shows an electrochromic device made using two substrates 54 with their conductive sides facing inwards.
  • the busbars for the two opposite electrodes 56 and 58 are shown at a distance "W".
  • the shapes of the mirrors may be such that this distance may not be constant, thus average numbers may be used.
  • the EC device size may be measured by measuring the width within the perimeter seal.
  • the thickness of the electrolyte layer for electrooptic devices made from this invention is generally less than 1 mm, and more preferably less than 0.5 mm. For automotive electrochromic mirrors this distance is preferably less than 0.25 mm, so that self-erasure rate is acceptable. Any value of leakage current is acceptable as long as the device colors uniformly and self-erasure occurs at an acceptable rate. Thus leakage current may be different for different sized devices.
  • the leakage current should preferably be lower than 0.5 niA/cm 2 of the active area of the device.
  • Polymerizable materials such as co-reacting monomers, addition-reaction monomers, as well as catalysts, initiators, etc., may be added to the electrolyte solution.
  • Monomers can be polymerized in-situ after introducing the electrolyte solution into the cavity, or solid films of electrolyte may be formed and then laminated between the conductive substrates. Also the composition of these additives depends on the method of processing, such as curing by thermal, UV or other radiative method.
  • the monomeric additives may become incompatible after polymerization, one has to be careful in exercising the choice of material. Details on materials, processing, etc. are described in U.S. Patent 6,245,262, and in U.S. Patent 5,940,201, both incorporated by reference herein. Generally, the preferred ones are based on epoxy, urethane and acrylic chemistry. To keep the shrinkage low for in-situ polymerization, the concentration of additives is typically below 25% of the solvent. Non-electrochemically active dyes (to give desired colors), surfactants and other modifiers may be added to the electrolyte solution, depending on the desired device characteristics and processability. These are described in the above references. As an example, near-IR absorbers have also been added (see: D.
  • EC devices of the present invention may contain other layers deposited on one of the electrodes. Schematics of these devices are shown in FIGURE 2 and FIGURE 3.
  • Device 34 shown in FIGURE 2 is similar to device 10 shown in FIGURE 1, except that device 34 includes additional electrochemically active layer 36.
  • Electrocliemically active layer 36 is deposited on either conductive layer 16 or conductive layer 18 (or on substrate 12 or substrate 14 if they are themselves conductive) or on both; for convenience, electrochemically active layer 36 is shown as deposited on second conductive layer 18.
  • Examples of materials used for preparing electrochemically active layers are tungsten oxide, Prussian blue, molybdenum oxide, vanadium oxide, polyaniline, polythiophene, polypyrrole, and derivatives and mixtures of these materials (devices made with these layers are described in U.S. Patent 4,671,619 to T. Kamimori et al. entitled "Electro-optic Device," which issued on June 9, 1987, and in U.S. Patent 5,729,379 to P-M.
  • electrochromic solution 30 will include an ionic liquid and at least one redox-active compound. For example, if tungsten oxide is used, which is a cathodic layer, then at least one anodic material (e.g., ferrocene, phenothiazine) is used in the electrolyte.
  • anodic material e.g., ferrocene, phenothiazine
  • the electrolyte may also contain salts of lithium, sodium and potassium, etc.
  • ions Li + , Na + , K "1"
  • the related anion is similar to, or the same as, the one of the ionic liquid solvent.
  • a material that combines the redox property of a dye and a source of lithium is lithium iodide salt (see, for example, U.S. Patent 4,671,619 to T. Kamimori et al. vide supra).
  • an anodic electrochemically active layer 36 is polyaniline, which can be used with a cathodic dye such as a viologen in the electrolyte solution of the invention.
  • a cathodic dye such as a viologen in the electrolyte solution of the invention.
  • One example is device 38, shown in FIGURE 3, which is identical to device 34 shown in FIGURE 2 except that electrochemically active layer 36 is further coated with an ion selective transportation layer 40, which allows the passage of smaller ions (lithium ion, for example) while blocking or retarding the passage of larger ions that are present in electrochromic solution 30.
  • Ion selective transportation layer 40 limits the back reaction and increases the memory of the devices. This is a useful feature for large windows as coloration is more uniform.
  • FIGURE 4 shows device 42, which is similar to device 34 of FIGURE 2, except that each of conductive layers 16 and 18 is coated with an electrochemically active layer.
  • FIGURE 4 depicts first conductive layer 16 as being coated with electrochemically active layer 44 and second conductive layer 18 coated with electrochemically active layer 36.
  • the other electrochemically active layer (layer 44 or layer 36), which is the counterelectrode (CE)
  • CE counterelectrode
  • the other electrochemically active layer may include polyaniline, nickel oxide, iridium oxide and vanadium oxide.
  • non-electrochromic layers that store ions are cerium-titanium and vanadium-titanium oxide. During the device assembly, one of these layers is typically pre-reduced or intercalated with cations, such as lithium.
  • the device changes its optical properties when the ions are ejected from the counterelectrode and injected in the electrochromic layer. For anodic electrochromic layers, ejection of charge also leads to a change in color.
  • Solution 30 in device 42 may include a UV stabilizer in addition to the ionic liquid solvent.
  • Solution 30 in device 42 may optionally include a salt that has cations that may be transported ftom the CE to the electrochromic layer and vice-versa. As an example if lithium is being intercalated in the electrodes, then a lithium salt may be added to the electrolyte.
  • One may even add a source of protons as long as the source of protons, typically an acid, is able to dissociate in the electrolytic medium.
  • the anion of the added salt should be preferably similar to the anion of the ionic liquid.
  • preferred lithium salts are lithium trifluoromethylsulfonate, lithium bis(trifluoromethylsulfonyl)imide, lithium bis(perfluoroethylsulfonyl)imide, and lithium tris(trifluoromethylsulfonyl)methide.
  • chromogenic devices that use electrolytes can also benefit from the electrolyte solutions of the present invention. These are called User Controlled Photocliromic Devices (UCPC) and photoelectrochemical devices (see, for example, U.S. Patent 6,246,505 to G. Teowee et al. entitled “Photocliromic Devices,” which issued on June 12, 2001, and C. Bechinger et al. "Photoelectrochromic Windows and Displays," Nature, vol. 383 (1996) pp. 608-610). In these devices, the coloration is photoactivated and may be controlled by the user. These types of devices could be similar in construction to device 42 shown in FIGURE 4.
  • the invention also includes a method for preparing electrooptic devices by vacuum backfilling.
  • electrooptic devices can be manufactured by vacuum-backfill techniques, including electrochromic, electroreflective, and electroluminscent devices; these include mirrors, windows, filters, lighted panels, and displays.
  • the electrooptic devices of the present invention may be conveniently manufactured using a vacuum-backfill method.
  • the negligible vapor pressures of ionic liquids allow vacuum-backfill techniques to be employed without the concerns of bubble formation and solvent contamination of the filling apparatus, as is the case with conventional non-ionic solvents. Further, and importantly, the negligible vapor pressure of ionic liquids even at elevated temperatures (see EXAMPLE 25) minimizes evaporation of solvent and any associated change in the concentration of the solutes dissolved in the solvent.
  • an empty cell (without electrolyte) with a fill port, and the electrolyte in a separate vessel, are placed in a chamber.
  • the chamber is evacuated, and the fill port of the cell is then lowered into the electrolyte while still under vacuum.
  • the chamber vacuum is then released while the fill port is still submerged in the electrolyte solution.
  • the viscosity of the solution is high (e.g. greater than 10 centipoise (cP))
  • the electrolyte solution is warmed by contacting the electrolyte solution with the warm, empty cell during the filling process; by warming the electrolyte or by conducting the filling operation in a heated chamber; or by some other means.
  • the ambient pressure on the electrolyte forces it into the cell.
  • FIGURE 5a-c shows a schematic representation of the vacuum backfill process.
  • Figure 5a shows the beginning of the process, after a vacuum has been established inside vacuum chamber 46.
  • Vacuum chamber 46 includes port 48 for evacuating, or introducing air or another gas (e.g., inert gas) into, chamber 46.
  • Chamber 46 may have other ports for introducing electrolytes and empty cells or other devices, which are not shown.
  • the chamber contains vessel 50, which holds electrocliromic solution 30.
  • Chamber 52 of the empty cell may be accessed through fill port 28. To start the backfilling process one or more empty cells along with the electrolyte is introduced in the chamber.
  • the electrocliromic solution 30 includes ionic liquids of the invention (and optionally a non- ionic co-solvent), one or more redox dye(s), and other additives such as UV stabilizers, polymerizable monomers, polymerization catalysts and/or initiators, etc.
  • the cell and electrochromic solution are kept apart while chamber 46 is evacuated. If the fill solution has an appreciable vapor pressure, as is the case with non-ionic conventional solvents as described in U.S. Patent 5,140,455 (vide supra), then the solvent will evaporate and prevent the establishment of a vacuum greater than the vapor pressure of the solvent.
  • the electrochromic solution has an appreciable vapor pressure, as is the case with non- ionic conventional solvents as described in U.S. Patent 5,140,455, then the evaporation of the solvent, especially under vacuum, and especially at elevated temperatures, may alter the concentration of solutes ftom their optimal values.
  • Ionic liquids used with the invention do not noticeably evaporate under conditions in which conventional solvents evaporate, and therefore the concentrations of the solutes do not change. Since the vapor pressure of the ionic liquids is negligible, the chamber is evacuated quickly, and further, electrolyte solution 30 is not consumed by the vacuum system.
  • the vacuum chamber may be quickly and efficiently evacuated, without consumption of solvent by the vacuum system or formation of bubbles. After establishment of the vacuum inside chamber, as shown in FIGURE 5b, fill port 28 of the empty cell is lowered into the electrochromic liquid 30.
  • the chamber vacuum is then released while the fill port is still submerged in the electrolyte (optionally, the chamber may be pressurized above atmospheric pressure) and the resulting pressure difference between the outside of the cell and the inside of the cell causes the electrochromic solution to fill the cell.
  • the filled cell is removed from vacuum chamber 46 and fill port 28 is sealed (for example, with an adhesive that cures thermally or by radiation such as UV radiation).
  • the vapor pressure of propylene carbonate, a possible additive is 0.03 mm of mercury at 20°C.
  • Sulfolane another possible additive, has a melting point of 27.6°C and a vapor pressure of 0.0062 mm at this temperature.
  • a vapor pressure lower than 0.003 mm of mercury, preferably lower than 0.001 mm of mercury under backfilling conditions is a negligible pressure.
  • Negligible pressure is defined by a test in which a solvent is placed in an open container with a 1.5 cm 2 opening under a vacuum of 0.1 mm Hg at 100°C for 1 hour. Under these conditions the loss of solvent due to evaporation should be less than 1 mg, and preferably less than 0.1 mg.
  • Other fill techniques besides the backfill process, such as those described in U. S. Patent 5,140,455 may also be used to manufacture the electrooptic devices of the present invention. These other fill techniques include injection fill techniques where the electrolyte under pressure is forced into the cavity.
  • the empty cell preferably includes more than one port, one for filling and another for venting gas as the cell is filled.
  • EC devices e.g., mirrors, windows and displays
  • Nanostructured materials of the present invention include coatings of particles less than 1000 nm in size, or coatings having pore sizes between about 2 nm and 1000 nm. Such coatings have high surface area.
  • Some examples of nanostructured materials include oxides of titanium, tungsten, zinc, tin and antimony. Nanostructured layers of these materials are deposited on conducting substrates such as ITO (indium-tin-oxide) and fluorinated tin oxide. High roughness tin oxides (such as TEC 8 from PILKINGTON in Toledo, OH) may serve both as transparent conductor and nanostructured semiconductor for dye attachment.
  • these attached dyes have anions, then it is preferred that they be similar to the anions described for the ionic liquid, dyes, and electrochromic solution of the present invention, the most preferred anions being trifluoromethylsulfonate (CF 3 SO 3 " ), bis(trifluoromethylsulfonyl)imide ((CF 3 SO 2 ) 2 N " ), bis(perfluoroethylsulfonyl)imide ((CF 3 CF 2 SO 2 ) 2 N ' ) and tris(trifluoromethylsulfonyl)methide ((CF 3 S O 2 ) 3 C " ) .
  • CF 3 SO 3 " trifluoromethylsulfonate
  • bis(trifluoromethylsulfonyl)imide (CF 3 SO 2 ) 2 N " )
  • bis(perfluoroethylsulfonyl)imide (CF 3 CF 2 SO 2 ) 2 N ' )
  • Nanostructured coatings may be used in photochromic devices employing electrochromic materials (see, for example, U.S. Patent 5,604,626).
  • a class of photochromic devices also known in the art as photo-electrochromic (PEC) devices, are devices where the electrochromic reaction takes place by converting the incident light impinging onto the device into an electrical voltage that automatically drives the electrochromic reaction.
  • PEC photo-electrochromic
  • These types of devices are used for applications that include windows and mirrors for architectural and automotive use.
  • window devices typically use two opposing substantially parallel, spaced apart electrodes (substrates with transparent conductive coatings facing inwards), one of which has a layer of a nanostructured, light-harvesting coating, typically made ftom nanosized particles of an oxide semiconductor such as titanium oxide or zinc oxide.
  • Nanostructured coatings may be coatings with pores or roughness in a range from about 2 nm to 1000 nm. These may then be optionally coupled with dyes to increase the efficiency of light harvesting and/or to drive the coloring or darkening reaction.
  • the second electrode or the light-harvesting electrode may have an electrochromic coating and/or the electrochromic material may be present in the electrolyte.
  • Nanostructured devices of the present invention may be user controlled (for an example of a user controlled photochromic device, see G. Teowee et al. in "User Controllable Photochromic (UCPC) Devices, Electrochimica Acta, vol. 44, (1999) pp. 3017-3026, incorporated by reference herein).
  • the user controls the external connectivity between the two electrodes using a conductor. If only the two electrodes are connected, for example, the device darkens when exposed to light.
  • Examples of prior art devices may be found in the following U.S. Patents: U.S. 5,604,626; U.S. 5,838,483; U.S. 6,246,505; U.S. 6,369,934; U.S. 6,118,572; U.S. 6,067,184; and U.S. 6,297,900.
  • Use of ionic liquids in electrolytes of these devices, and particularly the preferred ionic liquids described in this invention, would provide benefit in terms of device durability.
  • any added ionic dyes and salts to the electrolyte or to the electrodes should preferably have an anion similar to the anions of the ionic liquid. If more than one ionic liquid is present in the electrolyte with different anions, then at least one of these anions should match the anion of the ionic dye or the salt.
  • the present invention includes electroluminescent devices. These devices are typically constructed using two opposing substantially parallel, spaced apart electrodes (substrates with conductive coatings facing inwards, where one of them is transparent). The thickness of gap between the electrodes is typically in a range of 10 to 500 microns.
  • the electrodes may also be patterned for a display (the electrodes may have a coarse pattern or no pattern if used for a lighted panel).
  • Patterning includes pixelating, and the matrix formed may be a passive or an active matrix.
  • One of the electrodes may include reflective metal (e.g., platinum, rhodium, for example), or a transparent conductor (ITO or doped tin oxide, for example) with an underlying reflective coating (platinum, rhodium, aluminum, silver, and alloys of these materials, for example).
  • the resistivity of transparent conductor may be within 1 to 250 ohms/square and that of the reflective layers below 10 ohms/square.
  • the space between the electrodes is filled with an electrolyte, and the perimeter of the device is sealed.
  • the electrolyte used with these devices includes one or more dyes dissolved in an ionic liquid.
  • Electroluminescent devices are described, for example, in “Electrochemical Methods: Fundamental and Applications, Bard A. J., Faulkner, L.R., second edition Wiley, New York (2001).
  • the devices produce light when the when the reduced and the oxidized species that migrate away from the electrodes re- combine in the electrolyte.
  • the light may also be emitted at or near an electrode depending on the composition of the layers deposited at the electrode.
  • Some of these materials are dyes. Examples of active dyes are ruthenium tris- (2,2'bipyridine) and its derivatives.
  • Other materials are nanoparticles, in particular nanocrystals, of semiconductors. Nanocrystals of semiconductors are also referred to in the art as "quantum dots”.
  • nanoparticles are generally less than 10 nm, and more preferably less than 5 nm. These particles may be organically modified on the surfaces to avoid agglomeration and reactivity.
  • the active materials may be in the electrochemical coating or in the electrolyte.
  • amines and salts may also be present in addition to non- electrochemically active UV stabilizers.
  • Dyes that emit in near IR may be included to provide devices of the invention that can be used in special military operations.
  • One example of such a dye is heptamethine cyanine dye (S. K. Lee et al., Analytical Chemistiy, vol. 69, no. 20, (1997) pp. 4126-4133).
  • the electrodes themselves may consist of multiple-layers of semiconductors, metals and polymeric layers that may assist in the desired optical and electronic characteristics (e.g., work function) of the substrates.
  • the following EXAMPLES demonstrate the operability of the invention.
  • EXAMPLE 1 Absorbance spectrum of UV stabilizer in ionic liquid solvent.
  • BMI has higher absorbance in the UV (below 400nm) than BMP, due to its more conjugated nature.
  • the solution of BMI with 1% UV stabilizer was a clear liquid that did not form a precipitate at -30°C after 15 hours.
  • the absorbance spectra of the four solutions are shown in FIGURE 6.
  • EXAMPLE 2 Electrochromic window device with elec ⁇ 'olyte solution including redox dye. ITO substrate (15 ⁇ /sq) was cut into two 5.25" x 3.7" rectangular pieces. Two holes about 3 mm in diameter were drilled into one piece near the corners one of the diagonals. The substrates were then washed, dried and stored under clean room conditions.
  • An epoxy containing 105 micron glass bead spacers was dispensed around the edges of one of the substrates, and the second substrate was placed on top of it to make a cavity such that the two substrates were slightly off-centered along the long side of the rectangular edge.
  • the perimeter seal width was about 2 mm. This exposed edge on both substrates was later used to apply a busbar and make electrical connections.
  • the epoxy seal was cured at a temperature of 120°C.
  • the cavity was filled at room temperature with a liquid electrolyte solution containing 0.015 M of the charge transfer complex formed by N,N'- dimethylviologen bis(trifluoromethanesulfonyl)imide (methyl viologen imide salt), 0.015M N,N,N ,N -tetramethyl-l,4-phenylenediamine in l-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.
  • the two holes were plugged with Teflon balls (preferably the diameter of the ball is 5 to 30% bigger than the diameter of the hole) and further sealed using cover glass and an epoxy.
  • a solder strip was applied to the exposed ITO on each substrate along the long sides of the cavity using an ultrasonic solder. Electrical wires were then attached to these solder strips.
  • the electrochromic performance of the window device was determined by placing the device in a spectrometer and monitoring the color kinetics at 550 nm while a color potential of 1.0 volts was applied. This device colored uniformly to a deep blue color and reversed to the original colorless state upon bleaching by shorting the electrical leads from the two electrodes.
  • Figure 7 shows the spectra in the colored and the bleached state. The kinetic trace for the device is shown at 550 nm in Figure 8.
  • EXAMPLE 3 Electrochromic window device having a tungsten oxide coating.
  • Two half wave ITO substrates (15 ⁇ /sq) were prepared as described in EXAMPLE 2 except that the substrate that was not drilled into was coated with a 300 nm thick tungsten oxide coating (on the conductive side) containing 30 mole % of lithium oxide (based on tungsten atoms).
  • This coating was applied by a wet chemical method as described in U.S. Patent 6,266,177, incorporated by reference herein. Any other method such as chemical vapor deposition and physical vapor deposition could have been used to deposit the tungsten oxide layer.
  • the coating was fired at a temperature of 135°C in a humid atmosphere, and then at 250 °C in air. It was then fabricated into a cell as described in EXAMPLE 1. The cavity thickness was 175 microns.
  • the cavity was filled with electrolyte containing 0.1 molar lithium bis(trifluoromethanesulfonyl)imide, 0.015 M ferrocene, 1 weight percent of ethyl 2-cyano-3,3-diphenyl-acrylate (UVINUL® 3035) dissolved in l-butyl-3- methylimidazolium bis (frifluoromethanesulfonyl)imide and the fill holes were plugged as described earlier in EXAMPLE 1.
  • the electrochromic performance of the device was determined by placing the cell in a spectrometer and following the color kinetics at 550 nm while a color potential of 1.2 volts was applied followed by a bleach potential of -0.6 volts.
  • Electrochromic window device with an electrolyte solution of redox dye and UV stabilizer dissolved in ionic liquid solvent.
  • a device was prepare according to EXAMPLE 2 with the exception that it was filled instead with an electrolyte solution of N,N'- diethylviologen bis(trifluoromethanesulfonoyl)imide (0.015 M), ferrocene (0.015 M) and 1 weight % UVINYL® 3035 (BASF, Mount Olive, NJ) dissolved in BMP.
  • the cell was colored using 1.0 volt and had a transmission at 550 nm of 41%) and when shorted had a transmission of 76%.
  • Electrochromic window device with an electrolyte solution of redox dye and UV stabilizer dissolved in ionic liquid solvent.
  • a device was prepared according to EXAMPLE
  • EXAMPLE 6 A device was prepared according to EXAMPLE 2, with the exception that it was filled instead with an electrolyte solution having the composition of 0.015M of the charge transfer complex formed between N,N'-dimethylviologen dichloride hydrate and N,N,N ' ,N -tetramethyl-l,4-phenylenediamine and 1 weight percent of ethyl 2-cyano-3,3- diphenyl-acrylate (UVINUL® 3035) dissolved in l-butyl-3 -methylimidazolium bis (trifluoromethanesulfonoyl)imide. The cell was colored at 1.0 volt and shorted to bleach.
  • an electrolyte solution having the composition of 0.015M of the charge transfer complex formed between N,N'-dimethylviologen dichloride hydrate and N,N,N ' ,N -tetramethyl-l,4-phenylenediamine and 1 weight percent of ethyl 2-cyano-3
  • the bifunctional redox dye was the charge transfer complex formed by reacting 5,10-dihydro-5,10-dimethylphenazine (phenazine in Table 1 below) and N,N'- diethylviologen bis[bis(trifluoromethanesulfonoyl)imide] salt (viologen in Table 1 below).
  • the UV stabilizer was UVINUL® 3035.
  • the ionic liquid was BMP. Table 1 below includes the weight in grams of each component of the electrolyte solution. Table 1
  • Device 1 employed an electrolyte solution of ionic liquid and non-ionic additive propylene carbonate
  • device 2 employed ionic liquid without propylene carbonate
  • device 3 employed propylene carbonate without any ionic liquid.
  • the viscosity of the electrolyte in device 1 was 50 centipoise (cP) at 25°C and 8 cP at 82°C.
  • Tg of the electrolyte from the viscosity measurement was determined to be -140°C.
  • the electrolyte thickness of device 1 and 2 was 63 microns. For device 3 this was 175 microns.
  • the leakage current was so high that the device did not color uniformly; specifically the center did not color to the same extent as the edges.
  • the lealcage current decreased with increasing electrolyte thickness, while the other parameters are held constant. Results from these devices are shown in Table 2 below.
  • the transmission of the devices was measured using a fiber optic spectrometer at 550 nm while applying 0.9V for coloration.
  • the leakage current in Device 1 and 2 was lower than in Device 3 even considering the fact that the electrolyte thickness in Device 3 was 175 microns compared to 63 microns for the others. Also this shows that due to the increased leakage current the coloration of Device 3 was too shallow.
  • Electrochromic device with a bifunctional dye combining a viologen moiety and a ferrocene moiety was made in an interior rear- view mirror shape. This was approximately 25 cm in length and about 6 cm wide.
  • the substrates were
  • SUNGATETM 300 glass from PPG industries, Pittsburgh, PA
  • a conductive tin oxide coating having a resistance of 40.5 ohms/sq.
  • the electrolyte was backfilled through a hole left in the seal, which was plugged with a UV curing sealant after the filling operation.
  • the electrolyte thickness was 100 microns and the electrolytic solvent was ionic liquid (BMP) and PC mixture.
  • BMP ionic liquid
  • the electrolyte thickness was controlled by adding spacer beads to the perimeter seal material; the perimeter seal material is an epoxy resin.
  • the electrolyte composition was 2.502 g of ionic liquid, 0.2378 g of PC and 0.0973 g of a bifunctional redox dye Fc-Vio having a viologen moiety and a ferrocene moiety (l-(4-ferrocenylbutyl)- r-methyl-4,4' -Bipyridinium bis(trifluoromethanesulfonoyl)imide).
  • the dye anions were bis(trifluoromethanesulfonyl)imide.
  • EXAMPLE 10 Effect of electrolyte ionic concentration on devices with different conductivity transparent conductors. Six window devices of similar size were constructed following the procedures as described in EXAMPLE 2. Details of the electrolyte used are described below. The device size was 6.5 cm x 5 cm. The busbars were along the offset edges, which were 5 cm in length. The average active area of the device was about 54 x 43 mm.
  • ITO indium gallium
  • the electrolyte thickness was 88 micrometers and the EC dye concentration in the electrolyte was 0.05 molar.
  • the EC dye was a bridged dye with both an anodic and a cathodic moiety as described in EXAMPLE 9.
  • Ionic liquid used for this example was BMP.
  • the first set of three devices was constructed using ITO (about 13 ohms/square (half wave ITO)) for both substrates.
  • the second set of three devices was constructed using ITO having an electrical resistivity of 45 ohms/square.
  • the data in the first set of devices using 13 ohms/square is shown in Table 3 below:
  • Percentages of IL and PC are by volume. In concentration calculations it is assumed that there is no change in volume after mixing the IL and PC.
  • the devices were colored by applying 1.3 V across the two transparent conductors. All the devices were uniform in appearance both in the colored and the bleached state. The range is the difference between the colored state transmission and the bleached state transmission. All transmission values were recorded at 550 nm. The leakage current is measured as the current consumed in the fully colored state (steady state) at the applied coloring potential.
  • the ionic liquid (IL) used in the electrolyte was BMP and the co- solvent was propylene carbonate (PC).
  • EXAMPLE 11 High ionic concentration electrolytes employing solid salts. Electrolytes were made using Lithium bis(trifluoromethanesulfonyl)imide in PC. The salt concentration was 2 molar. The total ionic concentration including dye was 2.05 molar. Device sizes and all other parameters were similar to the ones in EXAMPLE 10. The devices when colored at 1.3 volts were uniform in appearance and the results are as shown in Table 4 below: Table 4
  • EXAMPLE 12 E#ect of cell gap (electrolyte thickness) and electrolyte composition. A set of nine cells was made with varying cell gap as shown in Table 5 below using only 45 ohms/square resistivity ITO.
  • the electrolyte included 0.05 molar EC bifunctional redox dye Fc-Vio having a viologen moiety and a ferrocene moiety (l-(4-ferrocenylbutyl)- -methyl-4,4'- Bipyridinium bis(trifluoromethanesulfonoyl)imide), which was also used in EXAMPLE 9.
  • the electrolyte solvent was a mixture of 60% IL and 40%) PC by volume.
  • the electrolytic solvent was 30:70. All other details were similar to that in EXAMPLE 10. Results when these devices were colored at 1.3 V are shown in Table 5 below. Table 5
  • EXAMPLE 13 Effect of Ionic Concentration in reflective devices.
  • the window cells made in EXAMPLE 10 were re-evaluated in a reflective mode by placing a silvered glass on their backs. In actual mirror application one of the outside surfaces of the cell would be silvered or a reflective conductor would replace one of the ITO conductors. The results are as shown in Table 6 below. Table 6
  • EXAMPLE 15 Effect of cell gap (electrolyte thickness) on reflective devices.
  • the set of nine cells described in EXAMPLE 12 were re-evaluated in the reflective mode.
  • the cells were made reflective as described in EXAMPLE 13. Results on these devices when colored at 1.3 V are shown in Table 8 below.
  • EXAMPLE 16 Examples of electrochromic reflective devices with a bifunctional dye combining a viologen moiety and a ferrocene moiety.
  • An EC window device was made in an automotive interior rear- view mirror shape.
  • the substrates were 45 ohm/square ITO coated glass plates in a thickness of 2.3 mm. This device was approximately 25 cm in length and about 6 cm wide.
  • the cell was made reflective by placing a silver coated glass reflector behind this device.
  • the dye used and the cell construction and filling is described in EXAMPLE 9.
  • the electrolyte thickness was 88 microns and the electrolytic solvent was ionic liquid (BMP) and PC mixture.
  • the dye concentration in the electrolyte was 0.05molar.
  • the composition of the electrolytic solvent was 30%) PC and 70% > IL by volume. Again assuming no volumetric change when these two components are mixed, the ionic concentration of the electrolyte was 2.37 molar. When this device was colored at 1.3V its reflection at 550 nm decreased from 81.8% to 7.7%. The leakage current on this device was 0.21 A/cm 2 . The coloring time was 8.5 and bleaching time was 20.6 seconds. Another device was constructed in a size of 6.5 x 5 cm as described in EXAMPLE 10 and then placed against a reflector as described above. A similar electrolyte was used in terms of solvent composition and the dye type, but the dye concentration was 0.075 molar and the cell gap was 53 microns.
  • the total ionic concentration was 2.4 molar. This device colored to a uniform state from 80.5% to 10% reflectivity when powered at 1.5volts in 8.6 seconds. It bleached on shorting in 8.2 seconds. The coloration and bleach times relate to 80% of the range as in other examples. The lealcage current in the colored state was 0.54 mA/cm 2 .
  • EXAMPLE 17 Effect of cell gap, dye concentration and total ionic concentration.
  • a set of 4 devices was prepared using a pair of 45 ohms/square ITO conductors as discussed in EXAMPLE 10 and EXAMPLE 13. These devices were only different in terms of electrolyte thickness and the composition of the electrolyte solvent as given below. These devices were colored by applying 1.3 volts and shorted for bleaching. All the devices were uniformly reflecting in the colored state. All measurements were at 550 nm. Data and results are presented in Table 9 below. Table 9
  • EXAMPLE 18 Devices with cobalt containing anodic dyes. Two anodic dyes, Co-phen and Co- terpy respectively were synthesized. The structure for Co-phen (top) and Co-terpy (bottom) are shown below.
  • NVF bis(trifluoromethanesulfonyl)imide
  • NTF bis(trifluoromethanesulfonyl)imide
  • These anodic dyes were made into electrolytes comprising of 70%BMP and 30% PC by weight as solvent.
  • the cathodic dye was diethylviologen bis(trifluoromethanesulfonyl)imide.
  • concentration of each, namely the anodic compound and that of the cathodic compound was 0.005 molar.
  • Two window devices were made (one with each dye) as described in EXAMPLE 10.
  • the electrolyte thickness was 88 microns and the transparent conductor was an ITO coating with a conductivity of 45 ohms/square.
  • the device with Co-terpy as anodic dye was orange in color in bleached state.
  • the devices were colored by applying a potential of 1.3 V.
  • the transmission values were measured at 550nm for all devices in this example.
  • the Co-terpy comprising device colored from 50% to 6% and appeared neutral in color to the eye in their dark state.
  • these anodic dyes may also be coupled to viologen dyes to give single bridged compounds with both anodic and cathodic functionality.
  • EXAMPLE 19 EC device. An EC window was constructed in a method and size similar to EXAMPLE 10.
  • the electrolyte was l-(ferrocenylmethyl)-r-methyl-4,4 l -Bipyridinium bis(trifluoromethanesulfonoyl)imide dye in propylene carbonate.
  • the ITO conductivity was 13 ohms/square and the electrolyte thickness was 100 microns.
  • the device colored reversibly in a range of 68% to 30%) at 550 nm. The coloration time was 3.4 seconds to cover 80% of this range.
  • EXAMPLE 20 Photochromic device A user controllable photochromic device was prepared with an electrochromic layer. Details on electrode and device preparation other than the electrolyte composition were according to Examples 1 to 3 in U. S.
  • Patent 6,246,505 incorporated by reference herein.
  • Substrates were TEC 10 glass from Pilkington (Toledo, OH).
  • the device size was 2" x 2.5" and the electrochromic electrode was amorphous tungsten oxide (formed at 250°C).
  • the light sensitive electrode was composed of crystalline titanium dioxide (titania) deposited from a colloidal dispersion.
  • the average titania coating thickness was 240 nm and that of tungsten oxide was 450 nm.
  • the cell gap i.e. the electrolyte thickness
  • the cell cavity was filled under nitrogen atmosphere with an electrolyte composed of 0.1 M lithium iodide in the ionic liquid 1 - butyl-3-methyl-pyrrolidinmm bis(trifluoromethylsulfonyl)imide.
  • the cell as filled had a transmission at 550 nm of 65%.
  • the transmission (at 550 nm) changed from 65% transmission to 46% transmission in 15 minutes.
  • the leads from the electrode were not connected, the cell transmission changed only from 65% transmission to 62% transmission after 15 minutes under similar sunlight exposure.
  • EXAMPLE 21 Photochromic device.
  • a user controllable photochromic device cavity was prepared Details on electrode and device preparation are as in EXAMPLE 20.
  • the cell cavity was filled under nitrogen atmosphere with an electrolyte composed of 0.1 M lithium iodide and 10 vol. % 3-butylpyridine in l-butyl-3-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide.
  • the device as filled had a transmission at 550 nm of 72.3 %.
  • the electrical leads from each electrode were shorted and the cell placed in sunlight the transmission changed from 72.3% to 37% transmission in 15 minutes. Under a bleach potential of 1.3 volts, the cell transmission changes from 37% to 66% transmission in 400 seconds.
  • EXAMPLE 22 Photochromic device.
  • a user controllable photochromic device cavity was prepared as described in EXAMPLE 20 with the exception that crystalline tungsten oxide was employed as the electrochromic layer; this layer was formed by heat-treating the coating to a temperature of 350°C. The coating thickness was 420 nm.
  • the cell cavity was filled under nitrogen atmosphere with an electrolyte composed of 0.1 M lithium iodide and 10 vol.% 3-butylpyridine in l-butyl-3-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide.
  • the filled device had a transmission at 550 nm of 74 %. When the electrical leads from each electrode were shorted and the cell placed in sunlight, the transmission changed from 74% to 38% transmission in 15 minutes.
  • EXAMPLE 23 EC device employing an electrolyte solution of ionic liquid solvent and bifunctional redox dye having cathodic moiety and europium anodic moiety.
  • a mixture of 1.0 grams of Eu(II) chloride and 2 equivalents of hydrogen bis(trifluoromethanesulfonyl)imide was heated until gas evolution stopped.
  • the product, Eu(II) bis(trifluoromethanesulfonyl)imide was then purified by heating in a vacuum at 60°C for four hours.
  • EXAMPLE 24 Synthesis of bifunctional redox dye and use in an EC device.
  • a mixture of 1- bromo-2-ethylhexane (1.2 g) and 4,4'-bipyridine (1 g) in acetonitrile (20 mL) was heated at 13 °C in a sealed tube for 24 hours to yield, after purification, 4-(2-ethylhexyl)-4,4'- bipyridine bromide (2 g).
  • 4-(2-ethylhexyl)-4'-methylenecarboxylate-4,4'-viologen bis(trifluoromethylsulfonyl)imide (602 mg) was mixed with Eu(II) .
  • bis(trifluoromethylsulfonyl)imide (518 mg), melted, and maintained as a melt for 15 minutes to form 4-(2-ethylhexyl)-4'-methylenecarboxylate(europium(II))-4,4'-viologen tris(bis(trifluoromethylsulfonyl)imide), which has the structural formula:
  • An electrochromic device using 4-(2-ethylhexyl)-4'-methylenecarboxylate(europium(II))- 4,4'-viologen tris(bis(trifluoromethylsulfonyl)imide) was prepared by dissolving 4-(2- ethylhexyl)-4'-methylenecarboxylate(europium(II))-4,4 , -viologen tris(bis(trifluoromethylsulfonyl)imide) (600 mg) in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP, 3 mL).
  • An EC device was prepared by placing the resulting electrolyte solution was placed in the chamber formed by an o-ring and two ITO electrodes.
  • the device successfully colored and bleached repeatedly upon cyclic applications of a voltage to the electrodes of the device, which presumably functions by oxidizing the Eu(II) to Eu(III) and reducing the diethyl viologen to the radical cation.
  • EXAMPLE 25 Weight loss of solvents in a vacuum. Propylene carbonate (1 g) was placed in a container having a surface area of 1.5 cm 2 , which was then heated to 100°C under a vacuum of 1mm Hg. After 1 hour, atmospheric pressure was restored and the vial was cooled to room temperature.
  • Butylmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide was prepared as follows: A solution of butylmethylpyrrolidinium bromide (50g) in deionized water (lOOmL) was prepared. Decolorizing charcoal or activated carbon (3g) was added to the solution, and the resulting mixture was boiled for three minutes, then cooled to room temperature and filtered. The filtrate (a purified solution of butylmethylpyrrolidinium bromide) was added to an aqueous solution (1 L) prepared from bis(trifluoromethylsulfonyl)amine (65g) and sodium hydroxide (9.25 g). The resulting mixture was stirred at room temperature for 3 hrs, after which two layers had formed.
  • Butylmethylimidazolium bis(trifluoromethylsulfonyl)imide was synthesized as follows: A solution ofbutylmethylimidazolium chloride (40 g) in deionized water (100 mL) was prepared. Decolorizing charcoal or activated carbon (3 g) was added to the solution, and the resulting mixture was boiled for 3 minutes and filtered. The filtrate was added to an aqueous solution (1 L) prepared ftom bis(trifluoromethylsulfonyl)amine (65 g) and sodium hydroxide (9.25 g). The mixture was stirred at room temperature for 3 hrs, after which two layers had formed.
  • the bottom layer containing butylmethylimidazolium bis(trifluoromethylsulfonyl)imide was separated away from the top layer, washed deionized water (3 x 50 mL), heated at 100°C under vacuum for 48 hrs, and then filtered through activated alumina to give anhydrous, highly pure, molten salt butylmethylimidazolium bis(trifluoromethylsulfonyl)imide.
  • the purity of the molten salt was assayed by cyclic voltammetry, absorbance spectroscopy or fluorescence measurements. This preparation procedure has the advantage that the materials can be made from the appropriate acid, which is less expensive than the corresponding lithium salt.
  • EXAMPLE 28 EC devices with bridged dyes.
  • Two devices were prepared using a bridged dye that included a cation having an anodic portion (phenazine) and a cathodic portion (viologen).
  • the cation has been described in "Electrochromic Dye System for Smart Window Applications," by Alexander Michaelis et al., Advanced Materials, vol. 13, pp. 1825-1828.
  • the bridged dye used in EXAMPLE 28 included the anion bis(trifluoromethanesulfonyl)imide (BMP).
  • BMP anion bis(trifluoromethanesulfonyl)imide
  • An epoxy containing 88 micron glass spacers was placed on the perimeter of one of the ITO substrates.
  • the second substrate was then placed on top of the epoxy coated ITO glass, in a position that was slightly off-center. Clamps were applied to the assembly at the perimeter to ensure intimate contact as well as to ensure that the cell spacing conformed to the spacer size in the epoxy.
  • the assembly was fired in an oven at 150°C for one hour to cure the epoxy, and then filled with electrolyte medium under a dry inert atmosphere by injecting the medium through one of the fill holes. Both the holes were subsequently sealed using a room temperature UV curing epoxy.
  • the dye concentration for both devices was 0.05 M. Busbars for powering were placed on the side of the substrate that was 2.5 inches long.
  • the conductivity of the ITO for both substrates was 13 ohms/square, and propylene carbonate (PC) was the solvent.
  • PC propylene carbonate
  • This device colored from 76% transmission to 5% at 550 mn.
  • the coloring time for 80% range was 8.4 seconds, and the bleach time was 26.8 seconds.
  • the conductivity of the ITO was 45 ohms/square ITO.
  • the solvent for the electrolyte was 70% n-butyl n-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMP) ionic liquid and 30% PC. This device colored from 74% to 21% at 550 mn.
  • the present invention includes durable electrochromic (EC) devices that can be fabricated using low conductivity transparent conductors and electrolytes, and have low leakage currents. These devices may be used for rearview mirrors, windows, displays, and the like, and exhibit high speed for coloration and bleach.
  • EC durable electrochromic
  • This invention also includes other types of EC devices, such as photo-electrochemical and electroluminscent devices.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
GB2436469A (en) * 2006-03-25 2007-09-26 Ionic Polymer Solutions Ltd Method of conduction using a quaternary ammonium compound
CN103896828A (zh) * 2012-12-28 2014-07-02 海洋王照明科技股份有限公司 双中心联吡啶类离子液体及其制备方法与电解液及锂离子电池
US9252459B2 (en) 2011-12-23 2016-02-02 Semiconductor Energy Co., Ltd. Ionic liquid, nonaqueous electrolyte, and power storage device
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Families Citing this family (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US7525716B2 (en) * 2005-03-04 2009-04-28 Ricoh Company, Ltd. Display device and display apparatus
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US9249492B2 (en) * 2005-11-07 2016-02-02 Micropyretics Heaters International, Inc. Materials having an enhanced emissivity and methods for making the same
US20070129568A1 (en) * 2005-12-06 2007-06-07 Ngimat, Co. Ionic liquids
US20080007086A1 (en) * 2005-12-10 2008-01-10 Ram Pattikonda Vehicle shading system and method using an electrically controlled transmission control material
KR101322847B1 (ko) * 2006-01-27 2013-10-25 삼성디스플레이 주식회사 고효율 유기전계발광소자
WO2007104144A1 (en) * 2006-03-10 2007-09-20 Transfert Plus, S.E.C. Compounds, ionic liquids, molten salts and uses thereof
US7990603B2 (en) * 2006-06-09 2011-08-02 Gentex Corporation Variable transmission window system
GB0623108D0 (en) * 2006-11-20 2006-12-27 Sericol Ltd A printable composition
US8593714B2 (en) * 2008-05-19 2013-11-26 Ajjer, Llc Composite electrode and electrolytes comprising nanoparticles and resulting devices
US8115984B2 (en) * 2007-06-18 2012-02-14 Ajjer Llc Laminated electrochromic devices and processes for forming the same
US8228159B1 (en) 2007-10-19 2012-07-24 University Of Central Florida Research Foundation, Inc. Nanocomposite semiconducting material with reduced resistivity
US8988756B2 (en) * 2008-01-31 2015-03-24 Ajjer, Llc Conductive busbars and sealants for chromogenic devices
US8599467B2 (en) * 2008-01-31 2013-12-03 Ajjer, Llc Environmentally safe electrochromic devices and assemblies
FR2928375B1 (fr) * 2008-03-05 2010-04-30 Essilor Int Composition de colorants photochromiques dans un solvant ionique.
WO2009140277A1 (en) 2008-05-15 2009-11-19 Johnson Controls - Saft Advanced Power Solutions Llc Battery system
DE102008024260B4 (de) * 2008-05-20 2010-04-15 Siemens Aktiengesellschaft Elektrochrome Formulierung und organisches elektrochrom schaltbares elektronisches Bauteil
US8790537B2 (en) 2008-06-09 2014-07-29 Council Of Scientific & Industrial Research Process for the preparation of solid polymer electrolytes using ionic liquids
US8514476B2 (en) 2008-06-25 2013-08-20 View, Inc. Multi-pane dynamic window and method for making same
US7619804B1 (en) * 2008-09-02 2009-11-17 Eclipse Energy Systems, Inc. Electrochromic polarizer
US7719751B2 (en) * 2008-09-17 2010-05-18 Soladigm, Inc. Electrical contact technique for electrochromic windows
KR101649290B1 (ko) * 2009-02-11 2016-08-31 삼성전자 주식회사 전기변색 소자 및 그 제조 방법
FR2948778B1 (fr) 2009-07-28 2011-08-12 Essilor Int Systeme electrochrome transparent
FR2950710B1 (fr) * 2009-09-28 2012-03-16 Essilor Int Systemes electrochromes transparents a plusieurs electrodes de polarisation
US9958750B2 (en) 2010-11-08 2018-05-01 View, Inc. Electrochromic window fabrication methods
US8643933B2 (en) 2011-12-14 2014-02-04 View, Inc. Connectors for smart windows
US10180606B2 (en) 2010-12-08 2019-01-15 View, Inc. Connectors for smart windows
EP3444664A1 (en) 2010-12-08 2019-02-20 View, Inc. Improved spacers for insulated glass units
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EP2652546A4 (en) * 2010-12-15 2014-09-10 Switch Materials Inc OPTICAL DEVICES WITH VARIABLE PERMEABILITY
US8950470B2 (en) 2010-12-30 2015-02-10 Poole Ventura, Inc. Thermal diffusion chamber control device and method
US8097085B2 (en) * 2011-01-28 2012-01-17 Poole Ventura, Inc. Thermal diffusion chamber
KR20140016298A (ko) * 2011-02-25 2014-02-07 에꼴 뽈리떼끄닉 뻬데랄 드 로잔느 (으뻬에프엘) 전기화학 및 광전자 소자를 위한 향상된 산화환원쌍
US9454055B2 (en) 2011-03-16 2016-09-27 View, Inc. Multipurpose controller for multistate windows
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CA2807615C (en) 2012-03-08 2020-06-30 Simplehuman, Llc Vanity mirror
US9341912B2 (en) 2012-03-13 2016-05-17 View, Inc. Multi-zone EC windows
US11635666B2 (en) 2012-03-13 2023-04-25 View, Inc Methods of controlling multi-zone tintable windows
US9405165B2 (en) 2012-03-30 2016-08-02 Gentex Corporation Controller configured for an electro-optic device and method thereof
WO2014032023A1 (en) 2012-08-23 2014-02-27 View, Inc. Photonic-powered ec devices
CA2915525A1 (en) 2013-06-18 2014-12-24 View, Inc. Electrochromic devices on non-rectangular shapes
WO2015051262A1 (en) 2013-10-04 2015-04-09 Gentex Corporation Variable transmittance window system
US11906868B2 (en) 2013-12-24 2024-02-20 View, Inc. Obscuring bus bars in electrochromic glass structures
CA2934277C (en) 2013-12-24 2023-09-26 View, Inc. Obscuring bus bars in electrochromic glass structures
US10884311B2 (en) 2013-12-24 2021-01-05 View, Inc. Obscuring bus bars in electrochromic glass structures
US10344208B2 (en) 2014-06-09 2019-07-09 iGlass Technology, Inc. Electrochromic device and method for manufacturing electrochromic device
US10294415B2 (en) 2014-06-09 2019-05-21 iGlass Technology, Inc. Electrochromic composition and electrochromic device using same
US9738140B2 (en) 2014-08-04 2017-08-22 Gentex Corporation Electrochromic devices
WO2016077918A1 (en) * 2014-11-17 2016-05-26 Switch Materials Inc. Photochromic-electrochromic compositions
US10076176B2 (en) 2015-03-06 2018-09-18 Simplehuman, Llc Vanity mirror comprising light sources and methods of manufacture thereof
US9766528B2 (en) 2015-03-09 2017-09-19 Gentex Corporation Electrochemical devices with plastic substrates
US10167073B2 (en) 2015-06-09 2019-01-01 Gentex Corporation Multi-piece bezel for electro-optic window assembly
US10589834B2 (en) 2015-06-09 2020-03-17 Gentex Corporation Retention of an electro-optic window assembly
CN108630820A (zh) * 2017-03-21 2018-10-09 北京大学深圳研究生院 一种交流平面有机电致发光器件
US10774198B2 (en) 2015-06-25 2020-09-15 Gentex Corporation Electrochromic thermoplastics, devices, and composites
JP6814805B2 (ja) 2015-11-20 2021-01-20 ジェンテックス コーポレイション プロトン可溶性有機エレクトロクロミック化合物
KR102162399B1 (ko) 2016-05-20 2020-10-06 젠텍스 코포레이션 전기-광학 윈도우 제어 시스템
US10869537B2 (en) 2017-03-17 2020-12-22 Simplehuman, Llc Vanity mirror
US11026497B2 (en) 2018-02-14 2021-06-08 Simplehuman, Llc Compact mirror
CN108490711B (zh) * 2018-03-12 2021-06-29 乐山师范学院 一种无边框电致变色镜片结构及其组装方法
CA3037704A1 (en) 2018-03-22 2019-09-22 Simplehuman, Llc Voice-activated vanity mirror
CN109110903A (zh) * 2018-09-18 2019-01-01 中国科学技术大学 一种水体中离子液体的处理方法
EP3887902A1 (en) * 2018-11-26 2021-10-06 View, Inc. Adhesive bus bars in electrochromic windows
USD925928S1 (en) 2019-03-01 2021-07-27 Simplehuman, Llc Vanity mirror
WO2020180627A1 (en) 2019-03-01 2020-09-10 Simplehuman, Llc Vanity mirror
USD927863S1 (en) 2019-05-02 2021-08-17 Simplehuman, Llc Vanity mirror cover
CN114667482A (zh) * 2019-10-02 2022-06-24 金泰克斯公司 电光元件和形成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0880568A1 (de) 1996-02-15 1998-12-02 Bayer Ag Elektrochromes system
EP1154311A1 (en) 1999-02-18 2001-11-14 Nippon Mitsubishi Oil Corporation Electrochromic element

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053571A (en) * 1977-01-31 1977-10-11 The United States Of America As Represented By The Secretary Of The Army Process for purifying lithium hexafluoroarsenate
US4671619A (en) 1984-07-24 1987-06-09 Asahi Glass Company, Ltd. Electro-optic device
US4902108A (en) 1986-03-31 1990-02-20 Gentex Corporation Single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof
US5355245A (en) 1988-02-12 1994-10-11 Donnelly Corporation Ultraviolet protected electrochemichromic rearview mirror
JPH0812361B2 (ja) * 1989-03-31 1996-02-07 日産自動車株式会社 エレクトロクロミック素子
US5140455A (en) 1989-11-29 1992-08-18 Donnelly Corporation High performance electrochemichromic solutions and devices thereof
US5142407A (en) 1989-12-22 1992-08-25 Donnelly Corporation Method of reducing leakage current in electrochemichromic solutions and solutions based thereon
FR2659871B1 (fr) * 1990-03-20 1992-06-05 Inst Francais Du Petrole Composition liquide non aqueuse a caractere ionique et son utilisation comme solvant. invention de mm. yves chauvin, dominique commereuc, isabelle guibard, andre hirschauer, helene olivier, lucien saussine.
US5500760A (en) 1991-09-06 1996-03-19 Donnelly Corporation Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same
US5910854A (en) 1993-02-26 1999-06-08 Donnelly Corporation Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices
US5729379A (en) 1994-10-26 1998-03-17 Donnelly Corporation Electrochromic devices
US5604626A (en) 1995-02-10 1997-02-18 Donnelly Corporation Photochromic devices
DE69635095T2 (de) * 1995-05-23 2006-05-18 Koninklijke Philips Electronics N.V. Redundantes Datenübertragungssystem mit mindestens zwei Kanälen
US5827602A (en) 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
GB9603851D0 (en) 1996-02-23 1996-04-24 Pilkington Plc Electrochromic devices
US6067184A (en) 1996-03-15 2000-05-23 Ecole Polytechnique Federale De Lausanne Electrochromic or photoelectrochromic device
EP0898730A4 (en) 1996-04-10 2001-09-26 Donnelly Corp ELECTROCHROMIC ELEMENTS
US6369934B1 (en) 1996-05-30 2002-04-09 Midwest Research Institute Self bleaching photoelectrochemical-electrochromic device
JP3955641B2 (ja) 1997-02-06 2007-08-08 ユニバーシティ カレッジ ダブリン エレクトロクロミック装置
US6141137A (en) 1998-08-26 2000-10-31 Gentex Corporation Electrochromic media for producing a preselected color
US5998617A (en) 1997-04-02 1999-12-07 Gentex Corporation Electrochromic compounds
US5940201A (en) 1997-04-02 1999-08-17 Gentex Corporation Electrochromic mirror with two thin glass elements and a gelled electrochromic medium
JPH10329479A (ja) 1997-05-30 1998-12-15 Pentel Kk 塗布具
AUPO816097A0 (en) 1997-07-22 1997-08-14 Sustainable Technologies Australia Limited Combined electrochromic and photovoltaic smart window devices and methods
DE19735732A1 (de) 1997-08-18 1999-02-25 Bayer Ag UV-geschützte elektrochrome Lösung
WO1999040025A1 (fr) 1998-02-03 1999-08-12 Acep Inc. Nouveaux materiaux utiles en tant que solutes electrolytiques
DE19824185A1 (de) 1998-05-29 1999-12-02 Bayer Ag Elektrochrome Anordnung auf Basis von Poly-(3,4-ethylendioxy-thiophen)-Derivaten in Kombination mit einer Lithiumniobat-Gegenelektrode
US6118572A (en) 1998-07-01 2000-09-12 The Regents Of The University Of California Photochromic, electrochromic, photoelectrochromic and photovoltaic devices
US6317248B1 (en) 1998-07-02 2001-11-13 Donnelly Corporation Busbars for electrically powered cells
DE19914304A1 (de) 1999-03-29 2000-10-05 Bayer Ag Elektrochrome Kontrastplatte
US6195192B1 (en) 1999-08-02 2001-02-27 Gentex Corporation Electrochromic materials with enhanced ultraviolet stability
US6188505B1 (en) * 1999-08-19 2001-02-13 Gentex Corporation Color-stabilized electrochromic devices
WO2001027690A2 (en) 1999-10-11 2001-04-19 University College Dublin Electrochromic device
US6266177B1 (en) 1999-11-18 2001-07-24 Donnelly Corporation Electrochromic devices
US6262832B1 (en) * 1999-12-03 2001-07-17 Gentex Corporation Anodic electrochromic materials having a solublizing moiety
US6614578B2 (en) 1999-12-03 2003-09-02 Gentex Corporation Ultraviolet stabilizing materials having a solublizing moiety
JP2001193363A (ja) 2000-01-05 2001-07-17 Kawamura Electric Inc 樹脂製窓枠のガラス脱落防止金具
US6392783B1 (en) 2000-02-24 2002-05-21 Gentex Corporation Substituted metallocenes for use as anodic electrochromic materials, and electrochromic media and devices comprising the same
US6531270B1 (en) * 2001-11-21 2003-03-11 Eastman Kodak Company Ionic liquids as coupler solvents in photothermographic systems
US6525861B1 (en) 2001-12-10 2003-02-25 Gentex Corporation Electrochromic device having a current-reducing additive
CN100386691C (zh) * 2002-06-21 2008-05-07 洛斯阿拉莫斯国家安全股份有限公司 含有离子液体的电光装置、电光汽车镜及其所用的电解液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0880568A1 (de) 1996-02-15 1998-12-02 Bayer Ag Elektrochromes system
EP1154311A1 (en) 1999-02-18 2001-11-14 Nippon Mitsubishi Oil Corporation Electrochromic element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1702236A4

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2436469A (en) * 2006-03-25 2007-09-26 Ionic Polymer Solutions Ltd Method of conduction using a quaternary ammonium compound
GB2436469B (en) * 2006-03-25 2010-10-06 Ionic Polymer Solutions Ltd Quaternary ammonium compounds and their uses
KR101751539B1 (ko) 2009-04-24 2017-06-27 도판 인사츠 가부시키가이샤 염료를 함유하는 청색 착색 조성물, 컬러 필터, 이것을 구비하는 액정 표시 장치 및 유기 ｅｌ 디스플레이
US9252459B2 (en) 2011-12-23 2016-02-02 Semiconductor Energy Co., Ltd. Ionic liquid, nonaqueous electrolyte, and power storage device
US10991984B2 (en) 2011-12-23 2021-04-27 Semiconductor Energy Laboratory Co., Ltd. Ionic liquid, nonaqueous electrolyte, and power storage device
CN103896828A (zh) * 2012-12-28 2014-07-02 海洋王照明科技股份有限公司 双中心联吡啶类离子液体及其制备方法与电解液及锂离子电池
CN103896828B (zh) * 2012-12-28 2016-06-01 海洋王照明科技股份有限公司 双中心联吡啶类离子液体及其制备方法与电解液及锂离子电池
WO2023205310A1 (en) * 2022-04-21 2023-10-26 Vitro Flat Glass Llc Electrochromic devices and compositions including anodic component anions
WO2023205336A1 (en) * 2022-04-21 2023-10-26 Vitro Flat Glass Llc Electrochromic devices and compositions including anodic components as cathodic component counter-anions

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US7119937B2 (en) 2006-10-10
EP1702236A2 (en) 2006-09-20
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US20050162728A1 (en) 2005-07-28
US20040257633A1 (en) 2004-12-23
EP1702236A4 (en) 2008-11-26
US6961168B2 (en) 2005-11-01

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