HK1124069A - An electro-optic device, an electro-optic automotive mirror comprising ionic liquids and the electrolyte used by them - Google Patents

Description

Electrooptical device containing ionic liquid, electrooptical automobile mirror and electrolyte used for electrooptical device and electrooptical automobile mirror

The present application is filed on 6/20/2003 under the name of 03817384.0 entitled "electro-optical device containing ionic liquid, electro-optical automobile mirror, and electrolyte solution used for the same".

Statement of federally government rights

The invention was made with the support of contract No. W-7405-ENG-36, the U.S. government has certain rights in the invention.

RELATED APPLICATIONS

This application claims priority from united states provisional patent application No. 60/390,611, filed on 21/6/2002 and entitled "electrolyte for an electro-optic device containing an ionic liquid," which is hereby incorporated by reference.

Technical Field

The present invention relates generally to electrolyte solutions and electro-optical devices, and more particularly to electrolyte solutions in which ultraviolet-resistant dyes are dissolved in ionic liquid solvents and electro-optical devices using the same.

Background

Electro-optical devices are devices that change their optical properties upon application of a voltage. The electro-optical device has multiple uses, for example, the electro-optical device can be used as an adjustable filter window of a building to control the absorption degree of solar energy of the building, and can also be used as an adjustable filter of an automobile. One particular form of electro-optic device is an electrochromic device, i.e. a device which changes colour upon application of a voltage.

Electrochromic devices have a reversible dimming function and have several uses. Applications include use as rear view mirrors for automobiles, trucks, buses, scooters and motorcycles, and as windows, eyewear, artificial light attenuation and conditioning tools, displays, contrast enhancement filters (including tunable filters for helmet mounted displays) for a variety of vehicles, other vehicles (including road, rail, marine and air vehicles) and buildings. To date, the only successful commercial application for electrochromic devices has been for automotive rear view mirrors. The high cost and poor durability limits the commercial application of electrochromic devices in the window field.

The disadvantage of the electrochromic device in terms of durability is caused to some extent by the electrolytes and solvents used in the prior art. The high dielectric solvents typically used in prior devices have one or more of the following drawbacks: high volatility, high sensitivity to humidity, hydrophilicity, poor electrochemical stability, high chemical activity, and susceptibility to degradation by light (typically by ultraviolet light). One requirement of the solvent used in the electrochromic device is that the other chemical components used in the electrochromic device are soluble and that these other chemical components are chemically stable with the solvent.

Recent advances in ionic liquid research have shown that the problems associated with conventional solvents can be solved by using organic ionic liquid solvents consisting of cations of ammonia and anions of the trifluorosulfonyl type. In addition to solving the problems described above, these solvents have a low flammability which makes the articles containing these organic solvents safer than articles containing conventional organic solvents.

The limitation of the use of ionic liquids for electro-optical devices is that many of the known components in electrochromic devices have some solubility in ionic liquids. Furthermore, the limitations inherent in known electrochromic dyes and additives are generally comparable to those inherent in conventional organic solvents, e.g., the electrochemical stability of these two classes of materials is comparable to the limitations inherent in conventional organic solvents, and thus, these dyes and other additives do not take full advantage of the advanced properties of ionic liquids. For example, WO01/93363 patent application by a.mcewen et al, japanese patent application No. 98168028 by m.watanabe et al, and us 6,365,301 patent by c.michot et al describe the use of ionic liquids; the patent application WO01/93363 entitled "nonflammable electrolytic solution", japanese patent No. 98168028 entitled "normal temperature molten salt and electrochemical device using the same salt substance", and us patent No. 6,365,301 entitled "material for use as electrolyte", which is exclusively for us granted No. 4/2 in 2002. The above three patents are hereby incorporated by reference. These documents and patents describe the use of ionic liquids in electrolytic solutions, but do not give specific details of the electrolyte components and the characteristics of electrochromic devices using these ionic liquids.

Therefore, there remains a need to invent certain more durable electro-optic devices.

It is therefore an object of the present invention to provide an electro-optical device having better durability.

It is another object of the present invention to provide an electrolyte solution for use in electro-optical devices.

It is a further object of the present invention to provide soluble dye compounds for use in ionic liquids in electro-optic devices.

Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

Summary of The Invention

In accordance with the objects and purposes of the present invention, as embodied and broadly described herein, the present invention includes an electrolyte solution having a glass transition temperature of less than about-40 ℃, the electrolyte solution including at least one bifunctional redox dye compound dissolved in an ionic liquid solvent. One type of redox dye compound useful in the present invention comprises a compound having a structureHalf of the redox active anode species and half of the redox active cathode species. Another type of redox dye compound contains half of the energy acceptor and the other half is either a redox active anode species or a redox active cathode species. Preferred cations for the ionic liquid solvent include lithium ions and quaternary ammonium ions, wherein the preferred quaternary ammonium ions are pyridinium cations, pyridazine cations, pyrimidine cations, pyrazine cations, pyrazoline cations, imidazole cations, thiazole cations, oxazole cations, triazole cations, tetraalkyl quaternary ammonium cations, N-methylmorpholine cations, and have the formula [ (CH)₃CH₂)₃N(R₁)]⁺Wherein R is₁Is alkyl with 2-10 carbon atoms and has a molecular formula of [ (CH)₃)₂(CH₃CHCH₃)N(R₂)]⁺Wherein R is₂Is alkyl with 2-10 carbon atoms and has a structural formula

Wherein R3 is an alkyl group having 2 to 10 carbon atoms and has the formula

Wherein R is₄Is an alkyl group having 2 to 10 carbon atoms, preferred anions include trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfo) methane anion ((CF)₃SO₂)₃C^-)。

The invention also includes an electro-optic device having at least one compartment and an electrolyte solution comprising a bifunctional redox dye compound, the electrolyte medium being located in the compartment, the bifunctional redox dye compound being dissolved in an ionic liquid, the electrolyte solution having a glass transition temperature below about-40 ℃. One type of redox dye compound used in the present invention contains half of the redox active anode species and the other half of the redox active cathode species. Another type of redox dye compound contains half of the energy acceptor and the other half is either a redox active anode species or a redox active cathode species. Preferred cations for the ionic liquid solvent include lithium ions and quaternary ammonium ions, wherein the preferred quaternary ammonium ions are pyridinium cations, pyridazine cations, pyrimidine cations, pyrazine cations, pyrazoline cations, imidazole cations, thiazole cations, oxazole cations, triazole cations, tetraalkyl quaternary ammonium cations, N-methylmorpholine cations, and have the formula [ (CH)₃CH₂)₃N(R₁)]⁺Wherein R1 is an alkyl group having 2 to 10 carbon atoms and has the formula [ (CH)₃)₂(CH₃CHCH₃)N(R₂)]⁺Wherein R2 is an alkyl group having 2 to 10 carbon atoms of the formula

Wherein R is₃Is alkyl with 2-10 carbon atoms, and has a structural formula

Wherein R is₄Is an alkyl group having 2 to 10 carbon atoms, preferred anions include trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-)。

The invention also includes dye compounds for use in electro-optic devices.

The invention also includes a method of filling an empty electro-optic device having relatively closely spaced plates, each plate having an electrically conductive surface on its inward facing side, the perimeter of the plates being sealed by a sealing medium which surrounds the area of each plate, using a thermionic liquid electrolyte solution. The filling method involves making a small hole in the sealing medium of the empty electro-optical device, placing the empty electro-optical device together with an electrolyte solution container containing an ionic liquid solvent into a chamber, and after evacuating the chamber, sinking the empty electro-optical device into the electrolyte solution with the sealed hole below the surface of the solution. At least a portion of the electrolyte solution is heated to at least 40 ℃. The hot electrolyte solution flows into the electrochromic device by exposing the solution to a pressure that is higher than the pressure inside the empty photovoltaic device. After the electro-optical device is filled with the electrolyte solution, the one aperture is closed.

Brief description of the drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention by way of example and together with the description, serve to explain the principles of the invention.

FIG. 1a is a cross-sectional side view of one embodiment of an electrochromic device in accordance with the invention.

FIG. 1b is a perspective view of an embodiment of the electrochromic device in FIG. 1 a.

FIG. 2 is a cross-sectional side view of an embodiment of an electrochromic device in accordance with the invention, wherein the electrochromic device includes an electrochemically active coating.

FIG. 3 is a cross-sectional side view of one embodiment of an electrochromic device in accordance with the invention, wherein the electrochromic device includes an electrochemically active coating and an ion-selective permeation layer.

FIG. 4 is a cross-sectional side view of an embodiment of an electrochromic device in accordance with the invention, wherein the electrochromic device includes two electrochemically active coatings.

Fig. 5a-c are schematic diagrams of a vacuum filling process.

Fig. 6 shows the absorption spectra of several solvents.

FIG. 7 shows the transmission spectra of an electrochromic device containing a redox dye in an electrolyte in the colored state and in the bleached state.

FIG. 8 illustrates the dynamic tracking of an electrochromic device containing a redox dye in the electrolyte.

FIG. 9 shows the transmission spectra of an electrochromic device comprising a layer of tungsten oxide in the colored and bleached states.

Fig. 10 illustrates a method of measuring the distance between bus bars according to an embodiment of the present invention.

Fig. 11 shows a graph of data used to determine the glass transition temperatures of ionic liquids and ionic and non-ionic solutions.

Figure 12 shows another data plot used to determine the glass transition temperatures of ionic liquids and ionic and non-ionic solutions.

FIG. 13 shows the absorption spectrum of the charge transfer complex and the absorption spectrum of the individual components.

FIG. 14 shows a cyclic voltammogram of a charge transfer complex between 5, 10-dihydroxy-5, 10-dimethylphenazine and the N, N-diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide in N-butyl-N-methylpyrrolidine cation bis (trifluoromethylsulfonyl) imide.

Detailed description of the invention

The present invention relates to an electro-optical device using an ionic liquid as an electrolyte solvent. Wherein the ionic liquid is a molten salt substance with a melting point at normal temperature or below normal temperature. For the purposes of the present invention, the terms "ionic liquid" and "molten salt" have the same meaning. Some of these salts are given in the article entitled "ambient ionic liquids consisting of alkylimidazoline cations and fluorine anions", published by R.hagiwara and Y.Ito in journal of the fluorine chemistry (105 th., 2000, pages 221-227). The ionic liquid solvent in the present invention does not include a mineral acid (such as sulfuric acid).

Only a few documents and patents suggest the use of ionic liquids in electrolytes (e.g., WO01/93363 patent application to a. mcewen et al, japanese patent No. 98168028 to m.watanabe et al, and us 6,365,301 patent to c.michot et al, 4/2.2002, wherein WO01/93363 patent application is entitled "nonflammable electrolyte", japanese patent No. 98168028 is entitled "normal temperature molten salt and electrochemical device using such salt species, and us 6,365,301 patent is entitled" material for use as electrolyte "). However, these documents and patents do not provide specific details of the electrolyte components used in electrochromic devices, nor do they describe the characteristics of electrochromic devices using these liquids.

The present invention relates to electrolytes and other components contained in electrochromic devices using ionic liquids as solvents and the structure of the electrochromic devices. The invention also relates to the use of ionic liquids in display devices in which a single electrode can be operated by an electrochromic device to produce and control images, text and other images. A process for manufacturing an electro-optical device will be described herein.

Careful screening of ionic liquids may result in a number of benefits including a broader range of electrochemical stability (greater than 4V, or in some cases greater than 6V), greater hydrophobicity, higher decomposition temperatures (the ionic liquids used in the present invention do not boil, but decompose at temperatures above 150 c, and more desirably at temperatures above 200 c), negligible vapor pressures (see, for example, c.m. gordon, "new advances in catalytic technology using ionic liquids" (222, 2001, page 101-, no absorption peak to light with the wavelength of 290-400 nm), and high conductivity.

Ionic liquids useful in the present invention include salts of organic cations combined with organic or inorganic anions. Preferred anions in the present invention include fluoride, triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion (N (CF)₃SO₂)₂ ^-) Bis (perfluorinated ethylsulfonyl) imide anion ((C)₂F₅SO₂)₂N^-) Tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-) Tetrafluoroborate ion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) And hexafluoroarsenate anion (AsF)₆ ^-). Of these anions, the preferred anion is the triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion (N (CF)₃SO₂)₂ ^-) Bis (perfluorinated ethylsulfonyl) imide anion ((C)₂F₅SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). The most desirable anion is bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Because such anionic species are low cost and have high hydrophobicity. In the prior art, the bis (trifluoromethylsulfonyl) imide anion is sometimes referred to as bis (trifluoromethylsulfonyl) amide or bis (trifluoromethylsulfonyl) imide and the formula is:

preferred molten salt organic cations for use in the present invention include: pyridine cation, pyridazine cation, pyrimidine cation, pyrazine cation, imidazole cation, pyrazoline cation, thiazoline cation, oxazoline cation, triazoline cation, but the preferred organic cations are not limited to these cations. Preferred ionic liquids based on quaternary ammonium cations are all ionic liquids having a glass transition temperature below-40 ℃, preferred ionic liquids are listed in U.S. patent nos. j.sun, m.forsgth and d.r.macfarlane, journal of physico-chemistry, entitled "normal temperature molten salts based on quaternary ammonium ions" (102 th, 1998, 8858-8864 p.) and 5,827,602 issued to v.r.koch et al at 27.10.1998; 5,827,602 entitled "hydrophobic ionic liquids," both of which are incorporated herein by reference.

Preferred ionic liquids contain tetraalkylammonium cations because the absorption of the ultraviolet spectrum by the ionic liquid consisting of these cations is minimal, which gives a fused salt based on these cations a stronger photochemical stability (see j. The quaternary ammonium cations used in the present invention can be substituted with hydrogen, fluorine, phenyl, alkyl groups having 1 to 15 carbon atoms, and other chemical substituents. The cation may even have a bridging structure.

The most suitable quaternary ammonium cation has the formula (CH)₃CH₂)₃N(R₁) Or is (CH)₃)₂(CH₃CHCH₃)N(R₂) Or structural formula is

Or a compound of the formula

A compound of (1); wherein R is₁Is an alkyl radical having 2 to 10 carbon atoms, R₂Is an alkyl radical having 2 to 10 carbon atoms, R₃Is an alkyl radical having 2 to 10 carbon atoms, R₄Is an alkyl group having 2 to 10 carbon atoms.

The most desirable ionic liquid solvent is N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide.

Since electrochromic devices can be used over a wide temperature range (e.g., automotive windows can withstand temperatures of-40 ℃ to 95 ℃ or higher), windows with high electrochemical stability can ensure that the electrochemical potentials for redox changes in the electrochromic material are within the stability range of the ionic liquid solvent even when these electrochemical potentials vary with temperature. The high hydrophobicity ensures that water does not become an integral part of the electrolyte and cause an irreversible electrochemical reaction.

The high boiling point and low vapor pressure of ionic liquids are very useful characteristics from the point of view of the manufacture of electro-optical devices. Most electrochromic devices are filled under vacuum (the vacuum filling process will be described in detail later). The low vapor pressure does not contaminate the vacuum system while ensuring the electrolyte composition is constant and does not retain bubbles during the filling process. This feature also enhances the chemical safety of the workplace. From the safety point of view, low flammability is very important, especially when the electro-optical device is applied to the building and transportation fields.

Preferred ionic liquid solvents for use in the present invention do not absorb substantial amounts of uv light at wavelengths above 290 nm and therefore, when exposed to uv light at these wavelengths, the ionic liquid solvents do not degrade into by-products which can lead to reversible discoloration, gas formation and/or the formation of electrochemically active/inert species.

Preferred ionic liquid solvents are those which provide a glass transition temperature of less than 0 ℃, preferably less than-20 ℃, and most preferably less than-40 ℃. As will be shown in example 8 (see below), the glass transition temperature can be determined from viscosity data.

In order to manufacture a practically applicable electrochromic device, several components need to be contained in the electrolyte. Depending on the structure of the device and its application, electrochromic devices may require uv stabilizers, other co-solvents (e.g., propylene carbonate, methyl sulfolane) and salts, redox dyes, viscosity modifiers, gelling materials, dyes with permanent color, including dyes that absorb light in the near infrared region (wavelengths between 700 and 2500 nm), and opacifiers. Several types of electrochromic devices, electrolyte solutions, and other components are described herein below. FIGS. 1-4 illustrate electrochromic devices containing liquid phase electrolytes or solid layered electrolytes.

Preferred embodiments of the present invention bear detailed reference notes. Similar or identical structures are identified by the same reference numerals. Fig. 1a and 1b are side and perspective views, respectively, of an embodiment of an electrochromic device in accordance with the invention. Devices of this construction are known in the art as single-chamber devices because the electrochemical activity is present only in a layer of material (i.e., electrolyte) between the conducting electrodes. Fig. 1a and 1b illustrate an electrochromic device 10 that includes a first substrate 12 and a second substrate 14. It should be understood that the substrate is not limited to any particular shape or material, for example the substrate may be made of plastic or glass, and one electrode may be made of an opaque substrate, for example metal, metal-clad plastic or metal-clad glass. Preferred metallic materials include aluminum, silver, chromium, rhodium, stainless steel, and silver alloys of silver with gold, palladium, platinum, or rhodium. Curved substrates may also be used. For convenience, a small flat glass sheet may be used as the substrate. Device 10 includes a first conductive layer 16 on first substrate 12 and a second conductive layer 18 on second substrate 14. The conductive layer is typically indium zinc oxide or fluorine-containing indium zinc oxide, but any other conductive coating may be used, for example a thin layer of metal or a thin layer of conductive polymer may also be used. If the second substrate 14 is not electrically conductive, e.g. made of glass or plastic, a conductive layer 18 needs to be used. However, the conductive layer 18 is optional if the second substrate 14 already has electrical conductivity, for example when the second substrate 14 is made of a metallic material, metal-clad glass or metal-clad plastic. When the second substrate 14 is conductive, the second substrate serves as both a structural substrate and a conductive layer. The electrochromic device 10 includes metal bus bars 20, one attached to the end of the first conductive layer 16 and the other attached to the end of the second conductive layer 18. The bus bar 20 may be directly attached to the second substrate 14 if the second substrate 14 has conductivity. A wire 22 is soldered or otherwise connected to each of the bus bars 20 to connect the bus bars to a power source (a battery or similar power source, not shown).

The bus bar 20 is made of a suitable conductive metal material and makes good conductive contact with a conductive layer or substrate. Specific bus bar materials include silver frit, solder alloys, metal bars, metal wires, and metal clips. Preferred bus bar fabrication materials include copper, copper alloys (such as copper-beryllium alloys), and tinned copper.

The electrochromic device 10 also carries a non-conductive gasket 24 that forms a seal between the first conductive layer 16 and the second conductive layer 18, or between the first conductive layer 16 and the second substrate 14 in the case where the compartment 26 does not use the second conductive layer 18. Preferably, compartment 26 has a width between the width of first conductive layer 16 and the width of second conductive layer 18, with a particular width of between about 20 microns and 5000 microns. More preferably, the width of the compartments is between about 40 microns and about 500 microns.

The gasket 24 is chemically stable to the molten salt electrolyte used in the present invention, is substantially impermeable to water and air (particularly oxygen and carbon dioxide), and is robust over a wide temperature range, preferably approximately in the range of-40 c to 100 c. The gasket 24 serves as an insulator between the two conductive surfaces, which allows substantially all of the current to flow through the electrolyte solution 30. In general, the thickness of the spacer 24 determines the distance between the first conductive layer 16 (i.e., the working electrode) and the second conductive layer 18 (i.e., the electrode opposite the working electrode), and determines the volume of the compartment 26 and the internal resistance of the device 10.

The apparatus 10 includes at least one port 28 through which a molten salt solution 30 is filled into the compartment 26. The port 28 may be located at any convenient location (e.g., the port 28 passes through the gasket 24, the first substrate 12, the second substrate 14). If a vacuum is used to fill compartment 26 with solution 30, only one port is required, but device 10 may have additional ports (e.g., with a pressure relief port) when other filling methods are used. After filling, the port 28 is closed.

The electrolyte solution 30 is a non-volatile and hydrophobic substance having a high concentration of cations and anions, thereby constituting minimal resistance to current flow. The solution 30 in compartment 26 is in electrically conductive contact with first conductive layer 16 and second conductive layer 18 (and second substrate 14 when second conductive layer 18 is not used).

The majority of the electrolyte solution 30 is an ionic liquid solvent. The solution 30 also includes at least one anode species and at least one cathode species. The anode species and the cathode species may each comprise half of a bifunctional redox compound. To improve the solubility of the anode species and cathode species in the ionic liquid solvent, the anode species and/or cathode species may be ionic species. Preferably, the relevant anion is the same as the anion in the ionic liquid solvent.

Preferably, the cation of the molten salt solvent is tetraalkylammonium, alkyl-substituted pyrrolidine or alkyl-substituted imidazole. A preferred fused salt anion is perchlorate anion (ClO)₄ ^-) Tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluoroethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-)。

The most preferred molten salt is N-butyl-N-methylpyrrolidinyl bis (trifluoromethylsulfonyl) imide.

Alternatively, the solution 30 may include a thixotropic agent, for example including a dispersed, electrochemically inert inorganic substance, such as silica or alumina, for ease of injection into the compartment 26.

The solution 30 may also contain one or more colorants to provide the desired color to the electrochromic device in the colored or bleached state.

The bifunctional dyes used in the present invention are stable under ultraviolet radiation. The solution 30 may contain other soluble uv stabilizers (see "world view of modern plastics" on "journal of chemistry" (2001), which is incorporated herein by reference).

The solution 30 may also contain one or more hardening agents to increase the viscosity of the solution 30 while maintaining conductivity. This is done to minimize the dispersion of the solution 30 if the device 10 is damaged. Hardeners include organic monomers and polymers such as poly (acrylonitrile), poly (vinylidene fluoride), poly (hexafluoropropylene), poly (vinyl alcohol), poly (vinyl acetate), poly (methyl methacrylate), and copolymers of these polymers, but the hardeners are not limited to these materials. These polymers may be polymerized in situ. These polymers can form crosslinks by polymerization of monomers (see, for example, U.S. patent No. 6,420,036 to d.v. varaprasad et al entitled "solid state films of electrochromic polymers, electrochromic devices made using these solid state films, and processes for making these solid state films and electrochromic devices," which was issued to its inventors on day 6 and 16 of 2002, the entirety of which is hereby incorporated by reference). For example, polymethyl methacrylate can be obtained by adding methyl methacrylate to a molten salt, followed by benzoyl peroxide to trigger the polymerization process.

Alternatively, the solution 30 may contain one or more soluble co-solvents that reduce the viscosity of the solution 30 and do not affect the durability and function of the color-changing mirror. Preferably, the co-solvent is inert to protons, has a high boiling point (preferably above 150 ℃), a low melting point (preferably below-30 ℃), and is present in solution 30 at a concentration of between about 0.5% and about 30%. Preferred co-solvents include propylene carbonate, N-methylpyrrolidone, perfluorodecalin and perfluorodecane.

Preferably, the device 10 may include a virtual reference electrode 32 that may measure the potential of the conductive layer 16. The virtual reference electrode 32 may be made of a metallic silver wire and inserted into the pad 24. Virtual reference electrode 32 is not in contact with conductive layer 16 or conductive layer 18 and may be in other forms. For example, a small portion may be separated from the conductive layer by etching an isolation line on the conductive layer 16 or the conductive layer 18, and the separated small portion may be used as a virtual reference electrode.

The present invention can be applied to standard multi-pane glazing by replacing one or more panes in the window with an electrochromic device in accordance with the present invention. The glass pane may be coated with a low emissivity material to block/attenuate ultraviolet, infrared and/or visible light.

There are a number of patents that describe electrochromic devices. Electrochromic devices using non-ionic liquid electrolytes are described in U.S. patent No. 4,902,108 to h.j.byker, on 20.2.1990, 5,998,617 to s.ramanujan et al, on 7.12.1999, and 6,045,724 to d.v. varpraad et al, on 4.4.2000; U.S. patent No. 4,902,108 entitled "single compartment, self-decolorizing solution phase electrochromic device and use of the solution in the device and use of the device," 5,998,617 entitled "electrochromic compound," 6,045,724 entitled "large area electrochromic window," is hereby incorporated by reference. Other patents that have described electrochromic devices using solid electrolytes include us 6,245,262 and us 5,940,201; united states patent No. 6,245,262 entitled "electrochromic polymer solid state films, electrochromic devices made using these solid state films, and processes for making these solid state films and devices," entitled "electrochromic mirror with two thin glass units and gelled electrochromic medium," entitled "united states patent No. 5,490,201 entitled" electrochromic polymer solid state films, electrochromic devices made using these solid state films, and processes for making these solid state films and devices, "and 1999, 8/17, incorporated herein by reference. In general, plasticizing a polymer with a liquid electrolyte can produce a solid electrolyte. The solvents described in these patents are neutral materials such as nitriles (e.g., glutaronitrile, 3-hydroxypropionitrile), sulfolanes (e.g., 3-methyl sulfolane), ethers (e.g., polyethylene oxide, polypropylene oxide, and glyme), alcohols (e.g., ethoxyethanol, ethanol), ethers and esters (e.g., gamma-butyrolactone, propylene carbonate, ethylene carbonate), and mixtures of these materials. While these patents list more detailed solvents and other ingredients, these patents do not describe the use of these ionic liquids.

The uv stability of the proposed electro-optic devices can be improved using uv filters and additives (see united states patent No. 5,864,419 to n.r. lynam at 26.1.1999, united states patent No. 6,122,093 to n.r. lynam at 19.9.2000, 6,362,914 to k.l. baumann et al at 26.3.2002, and united states patent No. 6,310,714 to j.r. lomprep et al at 30.10.2001, wherein united states patent No. 5,864,419 is entitled "infrared reflecting, uv blocking, and safety automotive electrochromic glazing", united states patent No. 6,122,093 is entitled "uv radiation reducing, safety protecting electrochromic glazing elements", united states patent No. 6,362,914 is entitled "electrochromic materials with greater uv stability and devices containing these materials", and united states patent No. 6,310,714 is entitled "electrochromic devices with stable coloration"). In U.S. patent No. 5,140,155, the solvent is selected for its uv absorbing properties, which was issued to d.v. varaprasad et al on 8/18 1992 entitled "high performance electrochromic solution and apparatus for using such solution". The least costly approach is to add a uv stabilizer to the electrolyte.

When the ionic liquids used in the present invention are uv-resistant materials, the electrochromic devices of the present invention containing these materials still require additional stabilizers to protect other components, such as polymers and dyes, while reducing light-induced electrode/electrolyte interactions. For the purposes of the present invention, UV stabilizers include those materials which absorb UV radiation and those which are capable of eliminating the species generated by UV irradiation, thereby minimizing damage caused by UV radiation. Any uv stabilizers and any other ingredients, including dyes, must be soluble in the electrolyte over the temperature range in which the device operates. Since electrochromic devices are used in most cases as mirrors, windows and facilities which are susceptible to weather factors, uv stabilizers must be suitable for a wide temperature range. Preferably, the minimum working temperature range of the electrochromic device is between 0 ℃ and 50 ℃, more preferably between-20 ℃ and 70 ℃, and most preferably between-40 ℃ and 105 ℃. Certain UV stabilizers can be found on pages C120-C122 of the "Presence plastics overview" publication by the society of periodicals, which is incorporated herein by reference. Some preferred UV stabilizers are benzophenone and its derivatives because these substances are compatible with a wide variety of ionic liquids (see "extraction of hydrogen from ionic liquids by triple excited states of benzophenone" (2001, 2364-2365) published by M.Muldon et al, chemical communications ", and" study of the kinetics of ionic liquids by pulsed radiolysis ", redox reactions in the solvents methyltributylammobis (trifluoromethylsulfonyl) imide and n-butylpyridinium tetrafluoroborate" (2002, 106, 3139-3147)), published by D.Behar et al, physico chemistry "). Other preferred uv stabilizers are benzotriazole (and derivatives thereof) and triazine (and derivatives thereof). The ultraviolet stabilizer accounts for 0.01-40 wt% of the molten salt solution, so that the freezing point of the electrolyte can be lowered by adding the ultraviolet stabilizer.

The uv stabilizers typically have an average absorbance of greater than 1 (90% uv attenuation) for uv light having a wavelength between 290 and 400 nm, and more preferably greater than 2 (99% uv attenuation), when measured over a 1 cm long path length and using an ionic liquid having about 1% by weight uv stabilizer. The ultraviolet absorptivity of the ultraviolet stabilizer can be obtained by subtracting the ultraviolet absorptivity of the liquid containing no ultraviolet stabilizer from the ultraviolet absorptivity of the solution containing the ultraviolet stabilizer.

Redox-active dye-containing compounds are described in the 2002/0012155 patent application by k.l. bauman et al and in the 6,344,918 U.S. patent by h.berneth, wherein the redox-active dye forms a bridging structure with an energy acceptor (i.e., an ultraviolet stabilizer) that allows the same molecule to both absorb ultraviolet light and act as a redox dye. 2002/0012155 patent application entitled "electrochromic materials with better uv stability and devices containing such materials", published on 31/1/2002; 6,344,918 entitled "electrochromic control Panel" entitled "by the applicant of U.S. patent application Ser. No. 2/5/2002, both of which are hereby incorporated by reference. For the purposes of the present invention, compounds of this type are generally referred to herein as "bifunctional redox dyes".

The advantage of using these bifunctional redox dyes (containing UV stabilizers in the specified range) is that the UV stability of the whole device is enhanced.

6,362,914, entitled "electrochromic materials having improved UV stability and devices containing such materials", which is assigned to K.Baumann et al, 2002, 3, 26, is hereby incorporated by reference. 6,362,914, which is prepared by combining an electrochromic dye with a uv stabilizer, is described as a cathode compound, which is referred to as the "energy acceptance point" in U.S. Pat. No. 6,326,914. Generally, the uv stabilizer comprises a benzophenone or a benzotriazole, and the uv stabilizer may be covalently bound to the anodic dye or the cathodic dye. The UV stabilizer in this compound absorbs UV light and prevents the other half of the dye in the compound from being damaged. 6,326,914 one such compound is specifically illustrated in the U.S. patent application Ser. No. 1-methyl-1- [ 1-benzotriazole-2-hydroxy-3-tert-butyl-5-propanoic acid propyl ester- [ benzene]]-4, 4-bipyridine bis (tetrafluoroborate). For the ionic liquid electrochromic device of the present invention, a different compound is used. In the compounds of the type used in the present invention, at least one tetrafluoroborate, and preferably two tetrafluoroborate anions, are replaced by a trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₃C^-) Substituted, most preferably with bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) And (4) substituting. For example, such compounds containing a bis (trifluoromethylsulfonyl) imide anion can be obtained by ion-exchanging the corresponding tetrafluoroborate anion compound with the bis (trifluoromethylsulfonyl) imide anion. Alternatively, such a compound can be obtained by subjecting an anode material in an ionic liquid containing a bis (trifluoromethylsulfonyl) imide anion to an electrochemical oxidation reaction, or by subjecting a cathode material (i.e., an electrochromic material) in the same ionic liquid to an electrochemical reduction reaction and a reoxidation reaction.

Specific cathode materials in the bifunctional redox dyes used in the present invention include materials defined by the following structural formula:

wherein R is₅Selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms and aryl groups having 5 to 10 carbon atoms. Optionally, R₅May contain one or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, olefin functionalities, and alkyne functionalities. In addition, the first and second substrates are,R₅and can also serve as a bridging structure for attachment to an energy receptor. R₆Selected from the group consisting of hydrogen, alkyl groups containing 1 to 10 carbon atoms, alkynyl groups containing 2 to 10 carbon atoms, and aryl groups containing 5 to 20 carbon atoms. Optionally, R₆May contain one or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, olefin functional groups, and alkyne functional groups. In addition, R₆And can also serve as a bridging structure for attachment to an energy receptor. R₇Can be selected from alkyl, ethyl, propyl or vinyl bridging groups containing 1 to 5 carbon atoms, wherein n is 0 to 4 and m is 0 to 2. Anion A^-Is a trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Anion B^-Is halogen anion, perchlorate anion (ClO)₄ ^-) Tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroarsenate anion (AsF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) Acetate anion (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Energy receptors include substances having the following structural formula:

wherein R is₇Selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms and aryl groups having 5 to 10 carbon atoms. Optionally, R₇May contain one or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, olefin functionalities, and alkyne functionalities. In addition, R₇And can also serve as a bridging structure for attachment to an energy receptor. In these formulae, n ═ 0 to 4 and k ═ 0 to 5. When properly bridged with an energy acceptor, the above-described cathode materials form bifunctional redox dyes, all of which are specific examples of bifunctional redox dyes in the present invention.

Specific anode materials in the bifunctional redox dyes used in the present invention include materials defined by the following structural formula:

wherein X and Y are independently selected from NH, NR₈、S、O。R₈Respectively selected from alkyl group having 1 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms and aryl group having 5 to 10 carbon atoms. Optionally, R₈May contain one or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, olefin functionalities and alkyne functionalities, and additionally, R₈And can also serve as a bridging structure for attachment to an energy receptor. R₉Respectively selected from alkyl group having 1 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms and aryl group having 5 to 10 carbon atoms. Optionally, R₉Can containOne or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, alkene functional groups, and alkyne functional groups, and further, R₉And can also serve as a bridging structure for attachment to an energy receptor. In these formulae, n-0-4 and k-0-2. The energy acceptor has the following structural formula

Or has the following structural formula

The substance of (1); wherein R is₇Selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms and aryl groups having 5 to 10 carbon atoms. Optionally, R₇May contain one or more ester groups, carboxylic acid groups, metal carboxylate groups, acyl groups, aryl groups, amine groups, urethane groups, ammonium groups, thioester groups, olefin functionalities, and alkyne functionalities. In addition, R₇And can also serve as a bridging structure for attachment to an energy receptor. In these formulae, n ═ 0 to 4 and k ═ 0 to 5. These compounds, which have both the anodic dye and the energy acceptor in the same molecule, are also specific examples of bifunctional redox dyes of the present invention, which when oxidized in an ionic liquid solvent, form free cations, the charge of which is in equilibrium with the charge of the anion in the ionic liquid solvent.

It is an important aspect of the present invention that the bifunctional redox dyes of the present invention are soluble in the preferred ionic liquid solvents of the present invention in the oxidized state, the reduced state, and any intermediate state. These dyes are reduced and/or oxidized in the device when a voltage is applied to the electrochromic device. This oxidation or reduction process is reversible. Furthermore, one or more oxidizing or reducing species may have a different color when compared to its previous state (prior to application of the voltage). It will be appreciated that these oxidising or reducing substances are also redox dyes. The dye that is reduced at the cathode is the cathode dye and the dye that is oxidized at the anode is the anode dye. In the device of the invention shown in fig. 1, several dyes may be present, but the electrolyte contains at least one cathodic dye and one anodic dye. Bifunctional redox dyes may contain both anodic and cathodic species in a single molecule, and this type of dye may undergo oxidation and reduction reactions at both electrodes.

In a preferred aspect, the bifunctional redox dye of the present invention comprises an electrochromic material, which is a cathodic material. Preferred electrochromic materials are N, N ' -diethyl electrochromic agents, N ' -dimethyl electrochromic agents and N, N ' -diphenyl electrochromic agents which are associated with fluorine-containing anions, for example with the tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroarsenate anion (AsF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-) It is related. Preferred anions are triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂S_O2)₂N^-) And tris (trifluoromethylsulfonyl)Methane anion ((CF)₃SO₂)₃C^-). Anode materials for the bifunctional redox dyes of the present invention preferably include metallocenes (especially ferrocenes), phenazines, phenothiazines, fulvalenes, 1, 4-substituted or 1, 2-substituted meta-phenylenediamines, and derivatives and combinations thereof. Some preferred phenazines are 5, 10-dimethylphenoxazine, 5, 10-dihydroxy-5, 10-diethylphenazine, 5, 10-dihydroxy-5, 10-dioctylphenozine or any other 5, 10-dihydroxy-5, 10-dialkylphenazine. Preferred m-phenylenediamine species are N, N, N ', N' -tetramethyl-m-phenylenediamine and N, N, N ', N' -tetramethyl-benzidine. The preferred fulvalene is tetrathiafulvalene. In connection with the ferrocene derivatives used in the present invention, see U.S. patent No. 6,317,248 and PCT application No. WO01/63350 to j.r. lomprep; agrawal, entitled "bus bar for electrochemical power cells", united states patent No. 6,317,248, entitled "substituted metallocenes for use as anodic electrochromic materials and electrochromic media and devices containing these germplasm", is assigned exclusively to 2001, 11/13/a, and WO01/63350, both of which are incorporated herein by reference. Preferred ferrocene species in the present invention include electron donating groups such as t-butyl ferrocene and decamethyl ferrocene linked to one or two cyclopentadienyl groups. Certain anodic dyes can be fluorinated to enhance the solubility of these anodic dyes in specific ionic solvents. In general, the concentration of the dyes (cathodic and anodic) is less than 0.1 molar, preferably less than 0.05 molar.

At least one of the anodic species or cathodic species in the bifunctional redox dye must be electrically tintable after absorption of electromagnetic radiation in the visible wavelength range in either the reduced or oxidized state. Since the dye component may return to an inactive form, the absorption of visible electromagnetic radiation is also reversible, meaning that the dye component either changes back to or returns to its previous state.

Two or more different dye compounds are used in electrochromic devices to control characteristics of such devices, such as controlling the color, kinetics, etc., of the devices (see U.S. patent No. 6,141,137, entitled "electrochromic medium for producing a predetermined color", issued 10/31/2000 to h.j.byker et al, which is hereby incorporated by reference). U.S. Pat. No. 4,902,108 describes the electrochemical properties to be considered in selecting dyes. Bifunctional redox dyes containing an anode species and a cathode species in the same molecule have recently been reported. Specific examples of such compounds are listed in united states patent No. 6,519,072, united states patent No. 6,241,916, and patent application No. WO 01/163350, in which united states patent No. 6,372,159 was issued to h.bernet et al at 4/16 of 2002, entitled "uv-protected electrochromic solution"; 6,519,072 to Nishikitani et al, entitled "electrochromic device"; 6,241,916 entitled "electrochromic System" and WO 01/163350 entitled Lomprey et al, was issued on 5.6.2001, which are hereby incorporated by reference. 6,519,072 and 6,241,916 describe dyes in which the anodic and cathodic dyes are not separate molecules, and are linked together in the same molecule to form an anodic dye moiety and a cathodic dye moiety in the same molecule. Thus, the cyclic voltammogram of a molecule, when measured from the raw state (i.e. when no electrochemical potential is applied), has at least one reduction peak and at least one oxidation peak derived from this compound. The reduction or oxidation is accompanied by an increase in the molar extinction coefficient, preferably both in the reduction and in the oxidation, at least one wavelength of visible light.

The bifunctional redox dye of the present invention comprises a cathode material and an anode material, wherein the cathode material forms a bridging structure with the anode material in a covalent manner. These compounds have good UV stability. Such a specific uv stable dye can be made by appropriately linking or bridging ferrocene to an electrochromic agent, which provides both anodic and cathodic redox dyes in an electrolyte for an electrochromic device using conventional non-ionic solvents.

Bifunctional redox dyes with anode and cathode moieties can form bridging structures with energy acceptor moieties to enhance uv stability. When used with the ionic liquid solvents of the present invention, these types of dyes can be used in electro-optic devices that are most useful in outdoor environments, whether in the colored or bleached state. Some improvements in uv stabilizers for conventional non-ionic solvents are described in U.S. patent application publication No. 2003/0030883 to p.giri et al, published 2/13/2003, entitled "uv stabilizing materials with solvency".

The present invention includes bifunctional compounds having an anodic moiety and a cathodic moiety, wherein one or more of the moieties is a cationic moiety in the as-received, oxidized or reduced state, the cationic moiety being via trifluoromethylsulfonate (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluoroethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane ((CF)₃SO₂)₃C^-) While charge balance is achieved, preferably, these cationic moieties are via bis (trifluoromethyliodoyl) imine ((CF)₃SO₂)₂N^-) Charge balancing is achieved. These compounds can be synthesized by anion exchange, for example, by reacting the salt species described in U.S. Pat. No. 6,519,072 (supra) with lithium bis (trifluoromethylsulfonyl) imide (Li (CF) dissolved in water₃SO₂)₂N) is reacted. Alternatively, certain compounds in which the cationic charge is in equilibrium with the bis (trifluoromethylsulfonyl) imide anion may be driven through the anodic species (i.e., bis) in an ionic liquid solventFerrocenes) in which the ionic liquid solvent contains bis (trifluoromethylsulfonyl) imide anions. These compounds in which the cationic charge is in equilibrium with the bis (trifluoromethylsulfonyl) imide anion can also be synthesized by electrochemical reduction and reoxidation of the cathode species (e.g., the mutagen) in an ionic liquid solvent containing the bis (trifluoromethylsulfonyl) imide anion. The invention also includes the use of these compounds in electro-optic devices.

In a preferred case, the cathode material of the bifunctional redox dye of the present invention includes an electrochromic agent (having a bipyridine cation pair structure) or anthraquinone, and the anode material has a pyrazoline, metallocene, phenylenediamine, benzidine, phenazine, phenoxazine, phenothiazine, or tetrathiafulvalene structure, or is a metal salt capable of being oxidized in an ionic liquid solvent.

The electrochromic compound having an anode substance portion and a cathode substance portion in the same molecule contains at least one anion which is the same as the anion in the ionic liquid solvent, and preferably, the electrochromic compound is an electrochromic agent having a bipyridine cation pair structure which exhibits a cathodic electrochromic property and has a structural formula:

the structure of the metallocene is:

and

the metallocenes exhibit anodic electrochromic characteristics. In these compounds, A^-Selected from the group consisting of trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Anion B^-Is halogen anion, perchlorate anion (ClO)₄ ^-) Tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroarsenate anion (AsF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) Acetate anion (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-)。R₁₀And R₁₁Each is a hydrocarbyl group selected from the group consisting of alkyl groups, alkenyl groups, and aryl groups having 1 to 10 carbon atoms. When R is₁₀Or R₁₁When aryl groups are present, these aryl groups may form fused rings with the cyclopentadienyl ring. m-0-4, n-0-4, Me represents chromium, cobalt, iron, manganese, nickel, osmium, ruthenium, vanadium, molybdenum (X) (Q), niobium (X) (Q), vanadium (X) (Q) or zirconium (X) (Q), wherein X and Q are selected from hydrogen, halogen, alkyl groups having 1 to 12 carbon atoms, perchlorates (ClO)₄ ^-) Tetrafluoroborate (BF)₄ ^-) Hexafluorophosphate radical (PF)₆ ^-) Hexafluoroarsenate (AsF)₆ ^-) Hexafluoroantimonate (SbF)₆ ^-) Acetoxy (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Specific alkyl groups are methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl and cyclohexyl. The aryl group is a phenyl group. Preferred alkyl groups are methyl, ethyl and propyl groups. When R is₁₀Or R₁₁When an aryl group is used, the aryl group may form a fused ring structure by bonding to the cyclopentadienyl ring, R₁₀Or R₁₁May be a group which crosslinks together two cyclopentadienyl rings in the metallocene structure. Preferably, m and n are 0 or 1, preferably 0. The preferred Me is iron.

Preferably, the electrochromic compound having an anodic species portion and a cathodic species portion present in the same molecule and containing at least one ion is a metallocene-bipyridine derivative having the formula:

wherein A is^-Selected from the group consisting of trifluoromethylsulfonate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Anion B^-Is halogen anion, perchlorate anion (ClO)₄ ^-) Tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroarsenate anion (AsF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) Acetate anion (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-)。R₁₀And R₁₁Each is a hydrocarbyl group selected from the group consisting of alkyl, alkenyl, and aryl groups having 1 to 10 carbon atoms. When R is₁₀Or R₁₁When aryl groups are used, these aryl groups may form a fused ring structure with the cyclopentadienyl ring, and in the same manner, m is 0 to 4 and n is 0 to 4. R12 and R₁₃Each of which is a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R₁₄Selected from the group consisting of alkyl, cycloalkyl, alkenyl, aryl, aralkyl having 1 to 20 carbon atoms and preferably 1 to 10 carbon atoms, heterocyclic group having 4 to 20 carbon atoms and preferably 4 to 10 carbon atoms, and hydrocarbyl group or heterocyclic group obtained by substituting hydrogen in the alkenyl group or heterocyclic group with a substituent. Me represents chromium, cobalt, iron, manganese, nickel, osmium, ruthenium, vanadium, molybdenum (X) (Q), niobium (X) (Q), vanadium (X) (Q) or zirconium (X) (Q), where X and Q are selected from hydrogen, halogen, alkyl groups having 1 to 12 carbon atoms, perchlorate (ClO)₄ ^-) Tetrafluoroborate (BF)₄ ^-) Hexafluorophosphate radical (PF)₆ ^-) Hexafluoroarsenate (AsF)₆ ^-)、Hexafluoroantimonate (SbF)₆ ^-) Acetoxy (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Specific hydrocarbon residues R₁₂And R₁₃Are hydrocarbon groups such as alkylene groups and various divalent groups having an ester bond unit, an ether bond unit, an amide bond unit, a thioester bond unit, an amine bond unit, a urethane bond unit or a silyl group in the hydrocarbon group. The divalent group having an ester bond unit is specifically represented by a group of the formula-R-COO-R-or-R-OCO-R-, wherein R is an alkylene group having 1 to 8 carbon atoms. A specific ester linkage unit is-C₄H₈-COO-C₂H₄、-C₄H₈-OCO-C₂H₄-、-C₄H₈-COO-C₄H₈-and-C₄H₈-OCO-C₄H₈-. The divalent group having an ether bonding unit may be specifically represented by a group of the formula-R-O-R-, wherein R is an alkylene group having 1 to 10 carbon atoms. The ether linkage unit is specifically-C₄H₈-O-C₂H₄and-C₄H₈-O-C₄H₈-. The divalent group having an amide bond unit is specifically represented by a group having a molecular formula of-R-CONH-R-or-R-NHCO-K-, wherein R is an alkylene group having 1 to 8 carbon atoms. A specific amide bond unit is-C₄H₈-CONH-C₂H₄、-C₄H₈-NHCO-C₂H₄、-C₄H₈-CONH-C₄H₈-and-C₄H₈-NHCO-C₄H₈-. The divalent radical having thioester bond units being composed ofA group of the formula-R-S-R-, wherein R is an alkylene group having 1 to 10 carbon atoms. A specific thioester linkage unit is-C₄H₈-S-C₂H₄and-C₄H₈-S-C₄H₈-. The divalent group having an amine bond unit is specifically represented by a group of the formula-R-NH-R-, wherein R is an alkylene group having 1 to 10 carbon atoms, and the divalent group having an amine bond unit is also represented by a group of 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. A specific amine linkage unit is-C₄H₈-NH-C₂H₄and-C₄H₈-NH-C₄H₈-. The divalent group having a urethane bond unit is specifically represented by a group of the formula-R-OCONH-R or-R-NHCOO-R-, wherein R is an alkylene group having 1 to 8 carbon atoms. A specific urethane linkage unit is-C₄H₈-OCONH-C₂H₄、-C₄H₈-NHCOO-C₂H₄-、-C₄H₈-OCONH-C₄H₈-and-C₄H₈-NHCOO-C₄H₈-. The divalent silyl-bearing group is 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. Specific silyl group is-C₄H₈-Si(CH₃)₂-C₂H₄-、-C₄H₈-Si(CH₃)₂-C₄H₈-、-C₄H₈-Si(C₂H₅)₂-C₂H₄-and-C₄H₈-Si(C₂H_s)₂-C₄H₈-. Specific alkyl radicals R₁₄Are methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl and n-heptyl radicals. A particular cycloalkyl group is a cyclohexyl group. Specific aryl groups are phenyl, tolyl, xylyl and naphthylAnd (4) a base. Specific alkylene groups are vinyl and allyl groups. Specific aralkyl groups are benzyl and phenylpropyl groups. Specific heterocyclic aromatic groups are 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, and isoquinolinyl groups.

When R is₁₄In the case of a substituted hydrocarbon residue group or heterocyclic group, specific substituents are alkoxy, alkoxycarbonyl, an acyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, halogen, cyano, hydroxyl, nitro and amino groups. Specific alkoxy groups are methoxy and ethoxy groups. The alkoxyhydroxy group is specifically represented by methoxycarbonyl. The acyl group is particularly represented by an acetyl group. Specific halogen groups are chlorine and fluorine. Specific substituted hydrocarbon residue groups are methoxyphenyl, chlorophenyl, fluorophenyl, methoxychlorophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl and methoxynaphthyl groups.

The metallocene-bipyridine bifunctional redox dyes of the present invention can be synthesized by first synthesizing the parent of the bifunctional redox dye, and then exchanging some or all of the anions; these bifunctional redox dyes are synthesized, for example, by suspending or dissolving the precursor in water and combining the precursor with an excess of lithium bis (trifluoromethylsulfonyl) imide. 6,519,072 describes precursors for bifunctional redox dyes. Then, the precipitate was collected and recrystallized to obtain a purified metallocene-bis (trifluoromethylsulfonyl) imide.

U.S. patent No. 6,241,916 to claussen et al describes bifunctional redox dyes having a covalent bridging structure separating an anodic species portion from a cathodic species portion. Many of these bifunctional redox dyes contain a base such as tetrahydroborate, perchlorate, methylsulfonate, tetrafluoromethylsulfonate, perfluorobutylsulfonate, phenylsulfonate, hexafluorophosphate, hexafluoroarsenate, hexafluorosilicate (SiF 6)^2-) Perfluorinated main group compounds, sulfonate groups and perchlorate, but none of the bifunctional redox dyes contains sulfonamide or perfluorinated sulfonamide. In contrast, the bifunctional redox dye of the present invention comprises at least one ion selected from the following anions: bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Preferably, all anions are bis (trifluoromethylsulfonyl) imide anions ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). More desirably, all anions are bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₃N^-) An anion. The invention also includes free cations together with these anions.

The electrochromic system of the present invention further comprises a liquid crystal display device having:

cation(s)₁-anions₁

Or has:

cation(s)₁-a bridging structure₁-anions₁

Or has:

cation(s)₁-a bridging structure₁-anions₁-a bridging structure₂-cations₂

Or has:

anion(s)₂-a bridging structure₂-cations₁-a bridging structure₁-anions₁

Bifunctional redox dyes of these structures, wherein the cation is₁And a cation₂Each represents a cathode material portion, an anion₁And anions₂Each representing a portion of anode material. Bridging structure₁And a bridging structure₂Respectively represent bridging units. These bifunctional redox dyes comprise at least one anion ((CF) selected from bis (trifluoromethylsulfonyl) imide₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-) The anion of (4). Preferably, all anions are bis (trifluoromethylsulfonyl) imide anions ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). More desirably, all anions are bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₃N^-) An anion. The invention also includes the free cations in these bifunctional redox dyes containing these anions. In the preferred case, the cation₁And a cation₂Respectively having the following structural formula:

the substance of (1); wherein R is₁₇And R₁₈Respectively represent a composition containing 1 toAn alkyl group of 18 carbon atoms, an alkylene group of 2 to 12 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, an aralkyl group of 7 to 15 carbon atoms or an aryl group of 6 to 10 carbon atoms, or R₁₇And R₁₈Together form- (CH)₂)₂-、-(CH₂)₃-or-CH ═ CH-these bridging structures, R₁₉、R₂₀And R₂₂～R₂₅Each represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a dentate, cyano, nitro or alkoxycarbonyl group having 1 to 18 carbon atoms, or R₂₂And R₂₃And/or R₂₄And R₂₅Forming a bridging structure of-CH-. R₂₆、R₂₇、R₂₈And R₂₉Each represents hydrogen, or two forms- (CH)₂)₂-、-(CH₂)₃-or-CH ═ CH-bridging structure. E₃And E₄Respectively represent O, N-CN, C (CN)₂Or N- [ aryl having 6 to 10 carbon atoms]。R₃₄And R₃₅Respectively represent hydrogen, alkyl containing 1 to 18 carbon atoms, alkoxy containing 1 to 18 carbon atoms, dentate, cyano, nitro, alkoxycarbonyl containing 1 to 18 carbon atoms or aryl containing 6 to 10 carbon atoms. R₃₀～R₃₃Each represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or R₃₀And R₂₆And/or R₃₁And R₂₇Forming a-CH-bridging structure. E₁And E₂Respectively represent O, S, N (R)₃₆)₂Or E is₁And E₂co-form-N- (CH)₂)₂-N-bridged structure, wherein R₃₆Represents an alkyl group having 1 to 18 carbon atoms, an alkylene group having 2 to 12 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms. Z₁Represents a direct bond, -CH ═ CH-, -C (CH)₃)＝CH-、-C(CN)＝CH-、-CCl＝CCl-、-C(OH)＝CH-、-CCl＝CH-、-C≡C-、-CH＝N-N-CH-、-C(CH₃)＝N-N＝C(CH₃) -or-CCl ═ N ═ CCl-. Z₂Is represented by- (CH)₂) r-or-CH 2-C6H4-CH2-, wherein r is 1-10. C^-Selected from bis (trifluoromethylsulfonyl) imide anions ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-)，D^-Selected from halogen anions, perchlorate anions (ClO)₄ ^-) Tetrafluoroborate anion (BF)₄ ^-) Hexafluorophosphate anion (PF)₆ ^-) Hexafluoroarsenate anion (AsF)₆ ^-) Hexafluoroantimonate anion (SbF)₆ ^-) Acetate anion (CH)₃COO^-) Methyl phenyl sulfonate anion (CH)₃(C₆H₄)SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) Or tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-) In which is bridged with a bridging unit₁And a bridging unit₂The bond formed is via the radical R₁₇～R₃₆And a radical representing a direct bond.

Anion(s)₁And anions₂Each represents one of the following structural formulae:

or anions₁Or anions₂Respectively represent metal salts containing titanium (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). R₃₇～R₄₃Each represents an alkyl group having 1 to 18 carbon atoms, an alkylene group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms, R₄₁～R₄₃And may also represent hydrogen, R₄₄～R₅₀Each represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen, a cyano group, a nitro group, an alkoxycarbonyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R is selected from₄₈～R₄₉May also represent a benzo-fused aromatic five-or six-membered heterocycle or a benzo-fused aromatic-like five-or six-membered heterocycle, R₅₀And may also represent N (R)₅₁)(R₅₂)。R₄₄And R₄₅And/or R₄₆And R₄₇Form- (CH)₂)₃-、-(CH₂)₄-、-(CH₂)₅-, or-CH-bridging structure. Z₃Represents a direct bond or a-CH-or-N-bridged structure, Z₄Denotes a direct double bond or ═ CH-CH ═ or ═ N-N ═ bridging structure. E₃、E₄、E₁₀And E₁₁Respectively represent O, S, NR₅₁、C(R₅₁)₂C ═ O or SO₂。E₅～E₈Respectively represent S, Se or NR₅₁(ii) a Wherein R is₅₁And R₅₂Each represents an alkyl group having 1 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms, an alkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aralkyl group having 6 to 10 carbon atomsAryl of a subgroup. R₅₃～R₆₀Each represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, an alkoxycarbonyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R₅₃、R₅₄、R₅₉And R₆₀Form- (CH)₂)₃-、-(CH₂)₄-, or-CH-bridging structure, V0-10, the bond formed with bridging unit 1 and bridging unit 2 being through radical R₃₇～R₅₄、R₅₉Or R₆₀And the aforementioned radicals representing direct bonds. Bridging unit₁Or bridging units₂Respectively represent a molecular formula of- (CH)₂)_n-or- (Y)₁)_s-(CH₂)_m-(Y₂)₀-(CH₂)_P-(Y₃)_Q-optionally, the two bridging units may be substituted with alkoxy groups having 1 to 4 carbon atoms, halogen or phenyl groups. Y is₁～Y₃Respectively represent O, S, NR₆₁COO, CONH, NHCONH, cyclopentadienyl, cyclohexadienyl, phenylene, naphthylene or beta-dicarbonyl. R₆₁Represents an alkyl group having 1 to 6 carbon atoms, an alkylene group having 2 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein n is 0 to 12, m is 0 to 8, p is 0 to 12, o is 0 to 6, q is 0 to 1 and s is 0 to 1.

It will also be appreciated that the invention also includes the free anion of the cathode compound described above, which is generated in situ during electrochemical reduction, and that it is necessary to include the ammonium cation in the ionic liquid solvent in order to achieve charge balance.

The electrochromic compounds of the invention also include bifunctional redox dyes having a redox-active cathode portion which imparts color characteristics to the dye 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 (V), antimony (III), antimony (V), bismuth (III), bismuth (V), cerium (III), cerium (IV), samarium (II), dysprosium (III), ytterbium (II), ytterbium (III), europium (II), europium (III). A specific example of this material, which contains a bipyridylium cation pair and europium, was prepared in example 12 (see below)

The electrochromic device of the present invention can be manufactured by an electrolyte solution consisting of an ionic liquid solvent, a redox active cathode dye (e.g., electrochromic agent) and a redox active metal, wherein the dye and the metal form a bifunctional dye in the form of a metal-arene complex (the "interaction of sigma donor/η 6-arene in europium and ytterbium mercaptide", published by m.niemeyer in the journal of european inorganic chemistry (2001, 1969-1981): experimental and computational studies "the article describes for metal-arene complexes).

The bifunctional redox dye existing in the form of metal-arene in the present invention has the molecular formula:

[ cation 1] [ M ]

Wherein M is a metal salt containing titanium (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). A specific such bifunctional dye was prepared in example 11 (see below).

Another class of redox dyes useful in the present invention are charge transfer compounds. Charge transport compounds are also sometimes referred to as charge transport complexes. The charge transport compound includes at least one electron rich aromatic compound and at least one electron poor aromatic compound, the electron rich compound and the electron poor compound combining in the ionic liquid solvent to form the charge transport compound. The uv-vis spectrum of the charge transfer compound is not a simple linear addition of the spectrum of the electron rich compound to the spectrum of the ion poor compound (see fig. 13), and the charge transfer compound has other properties, such as greater solubility. The green spectrum of the electron-transfer compound formed by combining 5, 10-dihydro-5, 10-dimethylphenazine, a white compound, and bis [ bis (trifluoromethylsulfonyl) imide ], a diethyl electrochromic agent, another white compound, in a ratio of 1: 1, contained an absorption range that was neither identical to that of 5, 10-dihydro-5, 10-dimethylphenazine nor that of N, N' -diethyl electrochromic agent bis [ bis (trifluoromethylsulfonyl) imide ].

The invention also includes the use of an electron transfer compound as an electrolyte solution and the use of an electro-optical device dissolved in an ionic liquid electrolyte solution. The invention also includes charge transport compounds comprising anions that are redox inert colorless anions wherein at least one anion is selected from bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-) The anion of (4). Preferably, at least one anion is bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-). More desirably, all anions are the same and are selected from bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₃N^-) Anion, bis (perfluorinated ethylsulfonyl) imide anion ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane anion ((CF)₃SO₂)₃C^-). Most desirably, the anion is only bis (trifluoromethylsulfonyl) imide anion ((CF)₃SO₂)₂N^-)。

Several other additives are used to modify the properties of the electrolyte solution of the present invention. One such additive is a viscosity modifier. Viscosity modifiers are soluble polymers or fillers such as fumed silica and finely divided alumina. Additives also include cosolvents, such as including other ionic or non-ionic liquids. Some additives are used to change the physical properties of the electrolyte solution, such as changing the melting point of the electrolyte solution. The additive may also change the electronic properties (response speed, current/time characteristics) of the electrolyte by changing the viscous resistance of the dye and thus the properties of an electro-optical device using such an electrolyte. 5,140,455 discloses additives that reduce current leakage or reduce back reaction. Although the ionic liquid itself has conductivity, other ionic substances such as solid salt substances can be added to the ionic liquid to lower the freezing point of the ionic liquid, change the conductivity of the ions, or make the ionic liquid have other characteristics (such as ions for intercalation), which will be described later. Further, the high concentration of the ionic substance can suppress the decoloring reaction.

Mixtures of conventional solvents (e.g., non-ionic solvents) with ionic liquids or mixtures of two or more ionic liquids may impart the electrolyte solution with the high ionic concentration characteristics of ionic liquids as well as the low viscosity characteristics of conventional solvents. The mixed solvent can control viscosity, change ionic conductivity, change freezing point, change kinetics of electrochromic reactions, change solubility (i.e., change solubility of added ingredients, such as dyes and uv stabilizers), improve processability, or impart other characteristics to the electrolyte solution. Generally, the volume of the conventional organic solvent in the electrolyte solution is preferably at least 80% or less, more preferably 30% or less, and most preferably 20% or less. Another way to express the ion concentration is the molar content, i.e. the number of ions contained per liter of solution. Preferably, the electrolyte solution should have a concentration of ionic species greater than 1 mole/liter, more preferably greater than 2 moles/liter, and most preferably greater than 3 moles/liter. When 1-butyl-3-imidazolidine bis (trifluoromethylsulfonyl) imide and propylene carbonate were mixed in a volume ratio of 80%/20% on the assumption that no change in volume occurred after the mixing, the resulting mixture had an ionic concentration of 2.7 mol. As shown in examples 8 and 9 (see below), the ionic liquid-conventional solvent mixing system has many advantages, such as lower glass transition temperature, better color consistency, and acceptable leakage (the leakage of the device is obtained by applying a stable voltage to the device and keeping the device in a fixed transparent or reflective state, and then measuring the current when the device is in a steady state).

Most desirable non-ionic co-solvents are propylene carbonate, ethylene carbonate, sulfolane, methyl sulfolane, and gamma butyrolactone. The nonionic solvents of 6,245,262 to varaprasad et al, which are referred to as plasticizers, include triglyme, tetraglyme, acetonitrile, propiophenone, 3-hydroxypropionitrile, methoxypropionitrile, 3-ethoxypropionitrile, butylene carbonate, glycerol carbonate, 2-acetylbutyrolactone, cyanoethylsucrose, gamma-butyrolactone, 2-methylglutaronitrile, N' -dimethylformamide, 3-methylsulfolane, methyl ethyl ketone, cyclopentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile, 3, 31-oxydepropanonitrile, 2-methoxyethyl ether, triethylene glycol dimethyl ether, or combinations thereof.

The self-erasing photochromic device shown in fig. 1 has excellent color uniformity. Devices of this construction contain at least one electrochemically active material, sometimes referred to as a redox active material or redox dye, which undergoes a redox reaction with a concomitant change in color. The device shown in fig. 1 is also referred to as a single compartment device, since all electrochemical reactions take place only in one compartment enclosed by the electrolyte layer and the gaskets contained in the two conductors. Self-extinction refers to the automatic recovery of the electrochromic process, which takes a short time after the device loses its starting power (generally, the electrochromic process takes only a few seconds or minutes, but the time of the electrochromic process can become longer depending on the composition of the electrolyte). The electrochromic device then reverts to the unpowered color state. The process of recovering the optical properties of the device is very rapid when not energized, for example, the recovery process takes less than 5 minutes, preferably less than 30 seconds. For electrochromic mirrors, these times refer to the time at which the color is erased and the degree of coloration reaches 50%. The required coloring and decoloring times depend on the use of the electrochromic device. Electrochromic windows can have longer tinting times and should have longer erasing times, a property sometimes referred to as open circuit memory, described in "durability problems and service life prediction for architectural electrochromic windows" (vol 56, 1999, p 419-436), published by a.w. czanclenna et al on solar materials and solar cells, which is incorporated herein by reference. Czanclenna et al describe many properties that electrochromic windows for construction should have. Electro-optic displays should have faster dynamics, for example, computer displays should have faster dynamics, while occasionally updated ensembles may have slower dynamics. The self-erasing action occurs because a reverse reaction occurs in the device in the energized state, the reverse reaction being determined by a leakage current that the device has in a steady state where the driving voltage of the device is constant and the degree of coloring is constant. Certain retroreactions are desirable for self-extinction, such as for automotive mirrors. However, some higher values may cause many other problems, such as the problem of causing color unevenness, which will be explained below. Higher ionic concentrations in the electrolyte solution can enhance the forward reaction, i.e., enhance the coloring effect, while the concentration of the ionic species and the viscosity of the electrolyte solution can slow the reverse reaction, i.e., slow the color loss. The fast forward and slow reverse reactions make the voltage distribution in the device more uniform and the coloration of the electro-optical device of the invention highly uniform. The uniformity of coloration afforded by the present invention is beneficial in several respects. First, uniform coloring allows for a larger device area, and the device will appear uniformly colored when power is applied to the device through conductors, typically bus bars, located on the perimeter of the device. In a typical device, as the area of the device increases, the ion concentration is relatively low, and the color of the region near the bus bar is darker than that of the middle portion. A second advantage of the conductivity of the ionic liquids used in the electrochromic devices of the present invention is that the voltage distribution throughout the device is more uniform, thus reducing the degree of electrophoretic separation of the redox dye in the activated state. In contrast, in an electrochromic device using a conventional nonionic solvent, when power is applied for a long time, for example, after power is applied for several tens of minutes or more, the electrophoretic separation action of the redox dye causes a colored band to be formed in the region near the bus bar. Third, the reverse reaction and the forward reaction do not uniformly increase with temperature, and thus, in the electrochromic device using the conventional non-ionic solvent, the rate difference between the forward reaction and the reverse reaction may be large, which may cause a device having a uniform color at 25 ℃ to have a non-uniform color at 40 ℃. Further, coloring unevenness increases as the device size increases, and most seriously, such coloring unevenness increases as the distance between the bus bar and the electrode farthest from the bus bar increases. The change in temperature particularly affects the mirrors outside the vehicle, which are generally larger than the mirrors inside the vehicle, and may need to be heated in cold weather to remove the mist, and the mirrors outside the vehicle may need to be colored in the daytime to reduce the glare of the sunlight, and thus improve the safety of the vehicle. As the size of the mirror increases, unevenness of coloring and unevenness of coloring due to temperature variation become more significant, and the problem in this aspect of the electrochromic device in the present invention is not serious as compared with the electrochromic device using a conventional non-ionic solvent.

The concentration of ionic species in the electrolyte of an electrochromic device is the sum of the concentrations of all salt species (i.e., containing anions and cations) including ionic liquids, salt species, dyes, and the like. Another method of determining the size of an electrochromic device is to determine the distance between two bus bars of opposite polarity as shown in fig. 10. The electrochromic device shown in fig. 10 uses two substrates 54 with conductive surfaces facing inward. The distance between the bus bars used for the two electrodes 56 and 58 is "W". This distance may not be constant due to the shape of the mirror; thus, the distance used is an average distance. Likewise, the electrochromic device can be sized by measuring the width within the perimeter seal. However, for most practical devices, the distance "W" does not vary significantly because the width of the seal or bus bars is increased by only a few millimeters on each side, with the distance "W" between the bus bars of the interior mirrors of the vehicle being about 5-8 centimeters and the distance between the bus bars of the exterior mirrors of the vehicle being about 7-20 centimeters. The electrolyte layer of the electrochromic device of the present invention is generally less than 1 mm thick, and more preferably less than 0.5 mm thick. For automotive electrochromic mirrors, thicknesses of less than 0.25 mm are preferred to achieve acceptable self-extinction rates.

As long as the coloration of the device is uniform and the self-erasing proceeds at an acceptable rate, no large leakage current is acceptable. Mirrors of different sizes will have different leakage currents. For an interior mirror size of about 25 cm x 6 cm, the preferred leakage current for the device operating area should be less than 0.5 milliamps per square cm.

Polymerizable materials such as co-reactive monomers, addition reactive monomers, and catalysts and initiators may be added to the electrolyte. The monomers may be polymerized in situ after the electrolyte is added to the device, or cured into a thin film and then delaminated. Likewise, the components added may also depend on the processing method, for example on thermal curing, UV curing or other radiation curing methods. Care must be taken in selecting the materials since the monomer additives may become incompatible after polymerization. 6,245,262 and 5,940,201 describe details of materials and processing. In general, preferred materials are based on epoxy-based chemicals, urethane-based chemicals, and acrylic chemicals. In order to provide low shrinkage for in situ polymerization, the concentration of the additive is typically less than 25% of the solvent.

Non-electrochemically reactive dyes (having a desired color), surfactants, and other modifiers may be added to the electrolyte solution depending on the desired device characteristics and processing characteristics. These aspects are discussed in the foregoing references. For example, near infrared absorbers may also be added to the electrolyte solution (see patent application No. WO 99/45081 to d.thieste et al entitled "near infrared absorbing electrochromic compounds and devices containing such compounds," which is incorporated herein by reference), so that when the devices are used as windows, the devices can absorb a greater range of solar energy.

The electrochromic device in the present invention may contain other layers of material deposited on one electrode. Schematic diagrams of these devices are shown in fig. 2 and 3. The device 34 shown in fig. 2 is similar to the device 10 shown in fig. 1, except that the device 34 is provided with an additional electrochemically active material layer 36. Electrochemically active material layer 36 is deposited either on electrically conductive layer 16 or on electrically conductive layer 18 (if substrate 12 or substrate 14 are themselves conductive, the electrochemically active material layer may be deposited on either substrate 12 or substrate 14), or both; for convenience, the electrochemically active material layer is shown deposited on the second conductive layer 18. Specific materials for the preparation of the electrochemically active material layers are tungsten oxide, Prussian blue, molybdenum oxide, vanadium oxide, polyaniline, polythiophene, polypyrrole, and derivatives and mixtures of these materials (4,671,619 U.S. patent and 5,729,379 U.S. patent describe devices made using these material layers; of which 4,671,619 is entitled "electro-optic device" entitled "by T.Kamimori et al on 6/9 1987; 5,729,379 is entitled" P.M.Allemand et al on 3/17 1998 entitled "electrochromic device", both of which are incorporated herein by reference).

The conductive layers 16 and 18 may themselves be divided into several layers. For example, a conductive layer of tin oxide may be deposited on top of the anti-iridescence coating. The electrochemically active material layer may be a composite formed of two layers of different materials.

In such a configuration, the solution 30 will include an ionic liquid and at least one redox active compound. For example, if tungsten oxide is used as the cathode layer, the electrolyte uses at least one anode material (e.g., ferrocene, phenothiazine). The electrolyte may also contain lithium salt, sodium salt, potassium salt, and other salt substances. Ions generated by the electrolyte during the coloring (Li)⁺、Na⁺、K⁺) Implanted into tungsten oxide in a reversible manner. Preferably, when such salts are used, the anion concerned is similar to or the same as an anion in the ionic liquid solvent. One material that has both dye redox properties and can act as a source of lithium ions is lithium iodide (see U.S. patent No. 4,671,619 to t.

The anode electrochemically active layer 36 is specifically composed of polyaniline, which may be used in conjunction with a cathode dye such as an electrochromic agent in the electrolyte solution of the present invention.

There are many other functional coatings that can alter the function of the device 34 shown in FIG. 2. One specific example is the device 38 shown in FIG. 3; device 38 is identical to device 34 except that a layer of ion selective transport membrane 40 is coated on electrochemically active layer 36. This ion selective transport membrane 40 allows lithium ions to pass through, but prevents or slows the movement of larger ions in the solution 30. The ion selective transport layer 40 limits the reverse reaction and improves the memory of the device. This is a useful property for large area windows as it results in a more uniform colouring of the window. 6,178,034, entitled "electrochromic device," which is assigned to p.m. allemand et al, 1/31 of 2001, which is incorporated herein by reference.

In some electrochromic devices, there may be two intervening layers as shown in FIG. 4. Fig. 4 shows device 42. device 42 is similar to device 34 except that the electrically conductive layers 16 and 18 of device 42 have electrochemically active material layers thereon. The first conductive layer 16 in fig. 4 is covered with an electrochemically active material layer 44 and the second conductive layer 18 is covered with an electrochemically active material layer 36. It is necessary that one of the electrochemically active material layers 44 or 36 be electrochromic and the other electrochemically active material (counter electrode) be electrochromic or simply store ions. If the electrochromic layer contains tungsten oxide or molybdenum oxide, the other layer of electrochemically active material may include polyaniline, nickel oxide, iridium oxide, and vanadium oxide. The specific non-electrochromic layer storing ions is composed of cerium-titanium oxide and vanadium-titanium oxide. During assembly of the device. One of these layers is typically pre-reduced or intercalated with cations such as lithium ions. When ions are emitted from the other electrode and enter the electrochromic layer, the optical properties of the device change. For an anodic electrochromic layer, the release of charge also causes a change in its color. The solution 30 in the device 42 may contain an ultraviolet light stabilizer in addition to the ionic liquid solvent. Alternatively, the solution 30 in the device 42 may contain a salt whose cations may move from the counter electrode into the electrochromic layer and vice versa. As a specific example, if lithium ions are inserted into the electrodes, a lithium salt may be added to the electrolyte. Even proton sources can be added to the electrolyte, provided that they dissociate in the electrolytic medium, usually consisting of acids. Furthermore, in a preferred case, the anions in the added salt species should be similar to the anions in the ionic liquid. Preferred lithium salts are lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, lithium bis (perfluoroethylsulfonyl) imide and lithium tris (trifluoromethanesulfonyl) methane. Specific electrochromic layers, counter electrodes and device components are given in the following patents: 6,266,177, 6,327,070, 6,172,794, 6,266,177 entitled "electrochromic device", 6,327,070, entitled "electrochromic device based on poly (3, 4-ethylenedioxythiophene) derivatives and lithium niobate counter electrodes", entitled "electrochromic element based on a poly (3, 4-ethylenedioxythiophene) derivative and a lithium niobate counter electrode", entitled "electrochromic element based on a poly (3, 4-ethylenedioxythiophene) derivative and lithium niobate counter electrode", was issued to p.m. almemand, 7,24, 2001; us patent No. 6,172,794 entitled "electrochromic device" was issued to m.s. burdis on day 1,9, 2001.

Other chromogen devices that use electrolytes may also benefit from the present invention. These chromogen devices are known as user-controlled photochromic and photoelectrochemical devices (see 6,246,505 U.S. patent and "photochromic windows and displays" published in nature by c.bechanger et al (383 th, 1996, pages 608-610), 6,246,505 U.S. patent No. 2001, 6.12.d, to g.teowee et al). In these devices, the coloring process is triggered by light and can be controlled by the user. These devices may be similar in construction to the device 42 shown in fig. 4.

The invention also includes a method of making an electro-optic device by a vacuum filling process. Many types of electro-optic devices, including electrochromic devices, electro-reflective devices, and electro-luminescent devices, including mirrors, windows, filters, light-emitting panels, and displays, can be fabricated by vacuum-filling techniques.

Electro-optic devices containing the ionic liquids of the present invention can be conveniently manufactured using vacuum filling techniques. Since the vapor pressure of the ionic liquid is negligible, there is no concern with vacuum filling that bubbles form and the filling equipment becomes contaminated with ionic liquid solvent, as is the case with conventional non-ionic solvents. Furthermore, it is important that the vapour pressure of the ionic liquid is very low even at elevated temperatures (see example 14), which ensures that the ionic solvent does not evaporate and thus does not lead to a change in the concentration of solute dissolved in the solvent.

As explained earlier, the vacuum filling method is a very attractive method for assembling an electro-optical device due to the low vapor pressure of the ionic liquid. In the vacuum filling process, an empty device unit (containing no electrolyte) with a charging port and an electrolyte contained in another container are placed in one compartment, and the compartment is subjected to a vacuum process. The charging port of the cell was then immersed in the electrolyte under vacuum. The vacuum of the compartment is then released in a state where the charging port is always immersed in the electrolyte solution. If the ionic solution has a high viscosity (e.g., greater than 10 centipoise), the electrolyte solution can be heated by contacting the electrolyte solution with a heat source, or by heating the electrolyte during the filling process, or by performing the filling operation in a heated compartment, or by other means. The ambient pressure to which the electrolyte is exposed causes the electrolyte to fill the device cell. The filled device unit is removed from the compartment and the filling opening is sealed.

Figure 5a shows the vacuum compartment 46. Air or gas, such as inert gas, is drawn or introduced into the compartment 46 through the passageway 48. Fig. 5a illustrates the filling process after a vacuum has been established in the compartment 46. The compartment 46 may be provided with other channels and elements for introducing electrolyte, which are not shown in fig. 5 a. The compartment includes a container 50 that holds the solution 30. The compartment 52 is formed by two substrates and a sealing plate (e.g., the compartment 26 is formed by the first substrate 12, the second substrate 14, and the sealing plate 24, each of which is coated). The sealing plate has a fill port 28 therein which is used to fill the compartment 52 with solution 30. The fill port 28 may be provided with one or more apertures. The substrate and the substance shown in figures 1-4 are bonded together before the compartment is formed. To perform the filling process, one or more empty cells are placed into the compartment along with the electrolyte solution. An ionic liquid solution 30 is also introduced into the vacuum compartment, wherein the ionic liquid 30 contains one or more ionic liquids, one or more redox dyes; optionally, the ionic liquid solution 30 may also contain a non-ionic co-solvent, one or more UV stabilizers, one or more in situ polymerizable monomers, and one or more polymerization catalysts and/or initiators. During evacuation of the compartment, the device unit and the ionic liquid solution are separated. If the fill solution has a relatively high vapor pressure, as is the case with the non-ionic conventional solvent described in U.S. patent No. 5,140,455, the solvent will evaporate and cause the vacuum pressure in the compartment to be no lower than the vapor pressure of the solvent. Also, if the conventional non-ionic solvent described in U.S. patent No. 5,140,455 is present, the fill solution has a relatively high vapor pressure, and the solvent evaporates; evaporation, especially under vacuum conditions and heating, can cause the concentration of the solute to deviate from its optimum value, since the ionic liquid does not evaporate under the conditions under which conventional non-ionic solvents evaporate, and therefore the concentration of the solute in the ionic liquid does not change. The process of establishing a vacuum in the compartment is fast due to the very low vapor pressure of the ionic liquid; furthermore, the vacuum system does not consume electrolyte. In addition, for conventional non-ionic liquids, bubbles are always present in the fill chamber, depending on the vapor pressure of the non-ionic liquid. A detailed discussion of the bubble phenomenon can be found in U.S. patent No. 5,140,455. Since the vapor pressure of the ionic liquid in the present invention is negligible, a vacuum state can be established rapidly and efficiently in the compartment, and the vacuum system does not consume solvent nor cause bubble formation. As shown in fig. 5b, the charging port of the cell is immersed in the ionic liquid with the compartment in a vacuum state, and then the vacuum of the compartment is released in a state where the charging port is always immersed in the electrolyte; alternatively, the compartment may be pressurised such that the pressure in the compartment is above atmospheric pressure. As shown in fig. 5c, the pressure difference between the inside and outside of the device cell causes the ionic liquid to fill the cell, fig. 5c shows the compartment 46 after the vacuum pressure has been replaced by an inert gas or air pressure, which is higher than the previously established vacuum pressure, preferably to restore the pressure in the compartment 46 to atmospheric or above atmospheric pressure. The filled device unit is taken out of the compartment and the charging opening is sealed with a heat-curable adhesive or an adhesive cured by ultraviolet irradiation. Propylene carbonate is a commonly used electrolyte material having a vapor pressure of 0.03 mm hg at 20 c. Sulfolane is also an additive for electrochromic devices, and has a melting point of 27.6 ℃ and a vapor pressure of 0.0062 mm Hg at its melting point. The vapor pressure of the ionic liquid can be ignored (see Gordon C.M., New progress of ionic liquid catalysis published in applied catalysis, 222, 2001, pages 101-117; Earle J.M., reaction in Diels-Alder ionic liquid published in Green chemistry, 1, 1999, pages 23-25). For the purposes of the present invention, vapor pressures below 0.003 mm Hg under the fill conditions are negligible pressures, and preferably below 0.001 mm Hg under the fill conditions. Whether the pressure was negligible was determined by a test in which the solvent was placed in an open container with a 1.5 square centimeter opening and held at 100 c for 1 hour under a vacuum pressure of 0.1 mm hg. Under these conditions, the amount of solvent lost by evaporation should be less than 1 mg, preferably less than 0.1 mg.

Other filling techniques, such as that described in U.S. patent No. 5,140,455, may also be used to make the electro-optic device of the present invention. These other filling techniques include an injection filling technique in which an electrolyte is pressed into a charging chamber by pressure. It is preferable that a hole is further opened in the charging chamber so as to discharge the gas in the charging chamber, or that the filling device has a degassing function.

The following examples demonstrate the performance of the invention.

Example 1: absorption spectra of UV stabilizers in ionic liquid solvents

According to the determination, the absorption spectra of propylene carbonate, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide and an N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide solution containing 1% of an ultraviolet stabilizer Uvinul 3035 (ethyl 2-cyano-3, 3-diphenyl acrylate, produced by Mount olive manufacturing company of New Jersey) are between 250 and 800 nanometers. 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide and N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide are all ionic liquid solvents useful in the present invention. 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide has better absorption of ultraviolet rays (wavelength less than 400 nm) than N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide due to higher conjugation. The solution of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide in combination with UV stabilizers is a transparent solution which does not form precipitates when left at-30 ℃ for 15 hours. Fig. 6 shows the absorption spectra of these 4 solutions.

Example 2: electrochromic window arrangement with electrolyte solution containing redox dye

The ITO substrate was cut into 2 rectangles of 5.25 inch × 3.7 inch. Two holes of about 3 mm diameter were drilled near opposite corners of the rectangle. The substrate is then washed, dried, and stored in a clean room. 105-micron glass beads containing epoxy substances are scattered on the periphery of the first substrate, the second substrate is placed on the first substrate, a cavity is formed between the two substrates, and the centers of the two substrates are slightly staggered in the long edge direction. Thus, the exposed edges of the two substrates can be used to place bus bars and make electrical connections. The epoxy sealing material is cured at 120 ℃. Filling the cavity with a liquid electrolyte solution at room temperature; the liquid electrolyte solution contained 0.015M of a charge transfer complex consisting of bis (trifluoromethylsulfonyl) imide, an N, N '-dimethylelectrochromic agent dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, and N, N' -tetramethyl-1, 4-phenylenediamine. After filling the cavity, two holes on the substrate are plugged with teflon balls (preferably the diameter of the ball is 5-30% larger than the aperture), and the cavity is further sealed with a glass lid and epoxy. And welding a welding strip on the exposed part of each substrate along the long side direction of the cavity by using an ultrasonic welding machine. Wires are then attached to these solder bars. The electrochromic properties of this window device were determined by placing the device in a spectrometer and monitoring the coloration kinetics of the device at 550 nm with an applied voltage of 1.0 volt. The device can be changed to a uniform deep blue color and return to the original colorless state after the wires of the two electrodes are shorted. Fig. 7 shows the spectra of the device in the colored state and the decolored state. FIG. 8 shows the kinetic tracking of the device at 550 nm.

Example 3: electrochromic window arrangement with tungsten oxide coating

Two ITO substrates were prepared as described in example 2, except that the substrate in this example was drilled and covered with a 300 nm thick layer of tungsten oxide (on the conductive side) containing 30 mole percent lithium oxide (based on tungsten atoms). This capping layer is formed by a wet chemical enrichment process described in U.S. patent No. 6,266,177. Other methods, such as chemical vapor deposition and physical vapor deposition, may also be used to form the layer of tungsten oxide on the substrate. The tungsten oxide layer was baked at 135 deg.C in a humid environment and then fired in air at 250 deg.C. The substrate was then fabricated into a device unit as described in example 1. The thickness of the cavity was 175 microns. The chamber was filled with an electrolyte containing 1% by weight of Uvinul 3035 dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide and the charging hole was closed as described in example 1. The device cell was placed in a spectrometer and observed for 550 nm coloration kinetics at 1.2 volts and-0.6 volts to determine the electrochromic properties of the device. The transmission of the cell for 550 nm wavelength light is 76% in the transmissive (achromatic) state and 12% in the fully colored state. Fig. 9 shows the transmission spectra of the device in the bleached state and in the colored state.

Example 4: comprising a redox dye dissolved in an ionic liquid solvent and electrochromic window device using ultraviolet stabilizer as electrolyte solution

The device was prepared according to example 2 except that the device was filled with an electrolyte solution formed from the N, N' -dimethyl electrochromic agent bis (trifluoromethylsulfonyl) imide (0.015M), ferrocene (0.015M) and 1% by weight Uvinul 3035 dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide. The device used a coloring voltage of 1.0 volt, a transmission of 41% for light of 550 nm wavelength in the colored state and 76% for this wavelength in the bleached state.

Example 5: comprising a redox dye dissolved in an ionic liquid solvent and electrochromic window device using ultraviolet stabilizer as electrolyte solution

The device was prepared according to example 2, except that the device was filled with an electrolyte solution formed from a charge transfer complex and 1% by weight of Uvinul 3035 dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide; wherein the charge transfer complex is formed by the reaction of dichloro N, N ' -dimethyl electrochromic agent hydrate dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide and N, N, N ', N ' -tetramethyl-1, 4-phenylenediamine (0.015M). The device has a coloring voltage of 1.0 volt, a conductivity of 19% in the colored state for light having a wavelength of 550 nm, and a conductivity of 70% in the bleached state for light having this wavelength.

Example 6: containing redox dyes dissolved in ionic liquid agents and ultraviolet stabilizer as a mirror device for an electrolyte solution system

The electrochromic mirror was manufactured using a substrate made of TEC15 (manufactured by LOF corporation, ohio), and the other electrochromic mirror was manufactured using indium-tin oxide. Silver is used to form a mirror on the non-conducting side of the TEC15 substrate. These substrates were assembled as described in example 2. The counter electrode drilled is an ITO electrode. A gap of the device unit; i.e. the width filling the electrolyte layer gap is 105 micrometers. After filling the device with an electrolyte solution consisting of bis (trifluoromethylsulfonyl) imide (0.015M), ferrocene (0.015M) and 1% by weight Uvinul 3035, which is a methyl electrochromic agent dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, a voltage of 1.0 volt was applied to the device to color it and the color was reduced by short-circuiting the electrodes. The reflectance of the device cell in the bleached state for light of wavelength 550 nm is 71%, and in the colored state the reflectance of the device for light of this wavelength is 26%. In the next place, the reflectance of the device for 550 nm wavelength light at 12 seconds was 50% of the reflectance range of 26% to 71%, and the time required for the device to reach 50% of the same reflectance range for 550 nm wavelength light in the decoloring process was 9 seconds.

Example 7: comprising a redox dye dissolved in an ionic liquid solvent and ultraviolet stabilizer as a mirror device for an electrolyte solution system

The device was fabricated as described in example 6, except that the device was filled with an electrolyte solution of 0.015M charge transfer complex and 1% by weight Uvinul 3035 dissolved in 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide; wherein the charge transfer complex is generated by the reaction of dichloro N, N ' -dimethyl electrochromic agent hydrate and N, N, N ', N ' -tetramethyl-1, 4-phenylenediamine. The device was colored at 1.0 volt and bleached in the event of an electrode short. The reflectance of the device in the achromatic state for light of 500 nm wavelength was 77%, and in the colored state for light of the same wavelength was 7.7%. When a voltage of 1.0 volt was applied to the device, the time required for the device to reach a degree of coloration of 50% was 1.6 seconds, and the time required for the device to reach a degree of coloration of 80% was 3.7 seconds.

Example 8: determination of the viscosity and glass transition temperature of Ionic liquids

The viscosity of a mixture of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide and propylene carbonate (volume ratio 90: 10) at different temperatures was determined using a cone and plate attachment on a Brookfield viscometer, model DV-III +. Fig. 11 and 12 show viscosity data for these liquids. These data were fitted to the following linear equation:

ln (viscosity) ═ A + B/(T-Tg)

Where T is the measured temperature (. degree. C.), Tg is the glass transition temperature (. degree. C.), and A and B are the fitting constants of the curves. The glass transition temperature can be determined by varying the assumed glass transition temperature until the correlation coefficient of the curve reaches a maximum value. For the fit in FIG. 11, the linear correlation coefficient (R)²) 0.996, for the solvent mixture shown in fig. 12, this correlation coefficient is 0.999. The best fit equation for 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is:

ln (viscosity) 601.41/(T-Tg) -1.483

Wherein the best fit point for the curve is at a point where the glass transition temperature is-85 ℃. The best fit equation for a mixture of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide and propylene carbonate is:

ln (viscosity) 967.35/(T-Tg) -2.694

Wherein the best fit point of the curve is at a point where the glass transition temperature is-130 ℃.

Example 9: comparison between electrochromic devices Using 3 different electrolyte solutions

Three devices were fabricated according to the method described in example 2. The working area of each device was 0.94 square centimeters. The bifunctional redox dye is a charge transfer complex consisting of 5, 10-dihydro-5, 10-dimethylphenoxazine (phenazine) and N, N' -dimethyl electrochromic agent bis [ bis (trifluoromethylsulfonyl) imide]Salt (electrochromic agent) reaction. The ultraviolet stabilizer is Uvinul^TM3035. The ionic liquid contains 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide. Table 1 lists the weight (in grams) of each component in the electrolyte solution

TABLE 1

Components	Device 1	Device 2	Device 3
				Ionic liquids	18.765	20.86	0
Propylene carbonate	1.7835	0	17.835
				Phenazine	0.1517	0.1517	0.1517
Electrochromic agent	0.5809	0.5909	0.5809
				Ultraviolet stabilizer	1.064	0.8633	0.9284

As shown in the above table, device 1 used an ionic liquid electrolyte solution and a non-ionic propylene carbonate additive, device 2 used an ionic liquid without propylene carbonate, and device 3 used propylene carbonate without any ionic liquid. The viscosity of the electrolyte in device 1 was 50 centipoise at 25 c and 8 centipoise at 82 c. The glass transition temperature calculated from the viscosity measurements was-140 ℃. The thickness of device 1 and device 2 was 63 microns. The thickness of the device 3 was 175 microns. When the thickness of the device 3 is reduced again, the leakage current of the device is so large that the device cannot be colored uniformly, especially the color in the center of the device is lighter than the color around. The leakage current intensity decreases with increasing electrolyte layer thickness, but the other parameters remain unchanged. The results for these devices are shown in table 2 below. The conductivity of these devices was measured using a fiber spectrometer when coloring with 0.9 volts.

TABLE 2

	Device 1	Device 2	Device 3
				Conductivity in the bleached state for 550 nm%	85	85	83
Conductivity in the colored state to 550 nm light%	21	20	31
				Leakage current (milliamp) in the fully colored state	27.6	19.8	44.4
Normal leakage current (milliampere/square centimeter)	0.29	0.22	0.47

Example 10: synthesizing a bifunctional redox dye; using solvents soluble in ionic liquids Electrochromic device of difunctional redox dye electrolyte solution

Chloromethyl ferrocene (1 g) was added to a solution containing 4, 4' -bipyridine (681 mg) dissolved in acetonitrile (20 ml). The mixture was heated in a sealed tube for 24 hours at a temperature of 130 ℃. The tube was then cooled and all solvent was removed under reduced pressure to give a yellow solid material; the yellow solid material was then washed with hot toluene liquid and subsequently dried to finally obtain the chloride of the methyl ferrocene electrochromic agent (1.6 g). These methyl ferrocene electrochromics chloride (1.6 g) was dissolved in acetonitrile liquid (20 ml) containing 5 ml of methyl iodide. The mixed liquid was heated at 100 ℃ for 24 hours, then cooled, and all the solvent was removed under reduced pressure. The resulting yellow solid was dissolved in water (100 ml) to make a clear solution. To this clear solution was then added lithium bis (trifluoromethylsulfonyl) imide (3 g). A black precipitate of N-methyl-N' -methyl ferrocene electrochromic agent bis (trifluoromethylsulfonyl) imide formed in the solution, and this black precipitate was isolated by filtration (yield 3.1 g). The resulting product is a bifunctional redox dye having the formula:

the redox dye is used for an electrochromic device, and the specific using process is as follows: dissolving the redox dye in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide, and then filling the solution into a cavity unit of an electrochromic device; wherein the cavity unit is composed of two ITO substrates and an O-shaped ring. The electrochromic device can be used for repeatedly coloring and decoloring by applying voltage in a circulating manner

Example 11: using an ionic liquid solvent and an anode material with a cathode material and europium Electrochromic device of electrolyte solution formed by bifunctional redox dye

A mixture of 1 gram of europium (II) chloride and 2 equivalents of bis (trifluoromethylsulfonyl) imide hydrogen was heated until no gas evolved. The product obtained by heating was europium (II) bis (trifluoromethylsulfonyl) imide, which was then purified by heating at 60 ℃ for 4 hours under vacuum. Europium (II) bis (trifluoromethanesulfonyl) imide (100 mg) and bis (trifluoromethanesulfonyl) imide (100 mg), an N, N' -diethyl electrochromic agent, were dissolved in N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide (2 ml). The resulting solution was loaded between two ITO plates. The resulting electrochromic device was successfully repeated with cyclic applied voltage, wherein the coloration and color reduction of the device was estimated to be due to the oxidation of europium (II) to europium (III) and the concomitant reduction of the diethyl electrochromic agent to the corresponding free cation.

Example 12: synthesis of bifunctional redox dyes and their use in electrochromic devices

1-bromo-2-ethylhexane (1.2 g) and 4,4 '-bipyridine (1 g) were dissolved in acetonitrile (20 ml), and the mixture was heated in a closed tube for 24 hours at 130 ℃ to purify the product to obtain 4- (2-ethylhexyl) -4, 4' -bipyridine as an smeller (2 g). A hydrated solution of 4- (2-ethylhexyl) -4, 4' -bipyridinium bromide (0.5 g), sodium hydroxide (40 mg) and 1-bromoacetic acid was refluxed for 12 hours, and then lithium bis (trifluoromethylsulfonyl) imide (500 mg) was added to the solution, which resulted in the formation of a white precipitate. The white precipitate was 4- (2-ethylhexyl) -4 '-methylenecarboxylate-4, 4' -electrochromism agent bis (trifluoromethylsulfonyl) imide, which was filtered and dried (620 mg of product produced). The structural formula of 4- (2-ethylhexyl) -4 'methylene carboxylate-4, 4' -electrochromism agent bis (trifluoromethylsulfonyl) imide is as follows:

the substance is used in an electrochromic device. 4- (2-ethylhexyl) -4 '-methylenecarboxylate-4, 4' -electrochromism agent bis (trifluoromethylsulfonyl) imide (602 mg) was mixed with europium (II) bis (trifluoromethylsulfonyl) imide and melted; the mixture was left in the molten state for 15 minutes, thereby producing 4- (2-ethylhexyl) -4 '-methylene carboxylate (4, 4' -electrochromism agent tris (bis (trifluoromethylsulfonyl) imide) europium), which has the formula:

an electrochromic device using 4- (2-ethylhexyl) -4 '-methylenecarboxylate-4, 4' -electrochromic agent europium bis (trifluoromethylsulfonyl) imide (600 mg) was prepared by dissolving it in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide (3 ml), and the resulting electrolyte solution was charged into a cavity formed by an O-ring and two ITO electrodes. The resulting electrochromic device was successfully repeated with cyclic applied voltage, wherein the coloration and color reduction of the device was estimated to be due to the oxidation of europium (II) to europium (III) and the concomitant reduction of the diethyl electrochromic agent to the corresponding free cation.

Example 13: synthesis of bifunctional redox dyes and their use in electrochromic devices

The charge transfer complex was obtained by mixing the N, N' -diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide with 1 equivalent of 5, 10-dihydro-5, 10-dimethylphenazine (total of 20 mg of the two compounds) in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide solvent (10 ml). A solution of the N, N' -diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide (20 mg) in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide (10 ml) was also prepared, and a solution of 5, 10-dihydro-5, 10-dimethylphenazine (20 mg) in acetone (10 ml) was prepared. The spectra of the three solutions were measured to be between 300 and 900 nm, and FIG. 13 shows the spectra of the three solutions. The spectrum of a solution of N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide of the N, N '-diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide is labeled with an "electrochromic agent", the spectrum of an acetone solution of 5, 10-dihydro-5, 10-dimethylphenazine is labeled with a "phenazine", and the spectrum of a solution of N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide of the N, N' -diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide and of the 5, 10-dihydro-5, 10-dimethylphenazine is labeled with a "charge transfer complex". The "charge transfer complex" spectra show new absorption bands at 450 nm, 665 nm and 730 nm, which are not present in the absorption spectra of the N, N' -diethyl electrochromic bis (trifluoromethylsulfonyl) imide or 5, 10-dihydro-5, 10-dimethenazine; the use of these two compounds is particularly suggested to form charge transfer complexes. The constitution of the complex is then confirmed by preparing crystals of the complex and detecting the structure of the crystals with X-rays. An electrochromic device was prepared as described in example 2, except that the cavity of the electrochromic device was filled with an electrolyte solution formed by dissolving the above-described charge transfer complex and 2-cyano-3, 3-diphenyl-acrylic acid ethyl ester (5% by weight) in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide solvent at 0.05M.

Electrochromic devices containing relatively low concentrations (0.03M) of the charge transfer complex and containing 2% 2, 4-dihydroxyphenol were also prepared, and these electrochromic devices were subjected to a set of cycling tests (79,500 cycling tests) at 70 c, and the electrochromic devices were exposed to 2,000 kilojoules of uv during the testing procedure, with the results showing no significant degradation in the performance of the electrochromic devices. As shown in FIG. 14, the voltammogram of the charge transfer complex between 5, 10-dihydro-5, 10-dimethylphenazine dissolved in N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide and the N, N' -diethyl electrochromic agent bis (trifluoromethylsulfonyl) imide shows only one reversible oxidation wave.

Example 14: weight loss of solvent under vacuum

Propylene carbonate (1 g) was added to a 1.5 square centimeter surface area vessel and the vessel was heated at 100 c under a 1 mm hg vacuum. After 1 hour, the pressure was returned to normal pressure and the vessel was cooled to normal temperature. The sample was then reweighed, with the remaining propylene carbonate weighing 0.627 g. A container having a surface area of 1.5 square centimeters was charged with the ionic liquid N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide (1 gram) and the container was heated at 100 c under a vacuum of 1 mm hg. After heating for 1 hour, the pressure was returned to normal pressure, and the vessel was cooled to normal temperature. The sample was weighed using a balance with an accuracy of 1 mg, and no change in the weight of the sample was observed.

Example 15: containing a multifunctional dye formed by combining an electrochromic agent and ferrocene Example of an electrochromic device

The electrochromic device is shaped as an interior rearview mirror. The mirror is about 25 cm long and about 6 cm wide. The substrate being Sungate^TM300 glass (manufactured by PPG industries, pisburg, pennsylvania) covered with a layer of conductive tin oxide having a resistance of 40.5 ohms/cm. The electrolyte is filled into the device through a small hole in the sealing plate, which hole is closed with a uv-curable sealant after the filling operation. The thickness of the electrolyte was 100 microns and the electrolyte solvent was a mixture of ionic liquid (1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide) and propylene carbonate. The thickness of the electrolyte is controlled by adding spacer balls around the perimeter of the sealing material, which is an epoxy resin. The electrolyte composition was 2.502 grams of ionic liquid, 0.2378 grams of propylene carbonate, and 0.0973 grams of a bifunctional redox dye, wherein the bifunctional redox dye was formed by combining an electrochromic agent and ferrocene. When the device was colored at 0.9 volts, its conductivity dropped from 79% to 16% for light having a wavelength of 550 nm. The test showed that the device in its decolorized state was exposed to 1,000 kilojoules of uv radiation at the uv radiation intensity specified by the society of automotive engineers J1960 test method, which indicated that the device had good uv stability.

In summary, the present invention includes UV stabilizers, bifunctional redox dyes, electrolyte solutions of these dyes dissolved in ionic liquid solvents, and electro-optic devices using these electrolyte solutions. These electrolytes generally have a glass transition temperature of-40 ℃ or lower, and these electrolyte solutions provide an electro-optical device with excellent durability and excellent performance.

The foregoing description of the present invention has been presented for purposes of illustration and description and is not intended to be exhaustive or limited to the invention in the form disclosed. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The example embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. The scope of the invention is defined by the claims appended hereto.

Claims (5)

1. A compound having the structure:

wherein A is^-Selected from the group consisting of the following anions: trifluoromethylsulfonate Ionic acid (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF3 SO)₂)₂N^-) Bis (perfluoroethylsulfonyl)) Imine ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane ((CF)₃SO₂)₃C^-)；B^-Selected from the group consisting of the following anions: anion of halogen element, perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, acetate, methylethylsulfonate, trifluoromethylsulfonate (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methane ((CF)₃SO₂)₃C^-) (ii) a Wherein R is₁O and R₁₁Are each selected from the following hydrocarbon groups: alkyl, alkenyl and aryl radicals having 1 to 10 carbon atoms, when R₁₀And R₁₁When the aryl group is an aryl group, the aryl group and the cyclopentadienyl group form a fused ring structure, wherein m is 0-4, and n is 0-4; r₁₂And R₁₃Each is a hydrocarbon residue having 1 to 20 carbon atoms, or an alkenyl group having an ester bond unit, an ether bond unit, an amide bond unit, a thioether bond unit, an amine bond unit, a carbamate bond unit, or a silyl group unit; r₁₄Selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, a hydrocarbon group or a heterocyclic group obtained by substituting hydrogen in the hydrocarbon group or the heterocyclic group with a substituent; me represents Cr, Co, Fe, Mn, Ni, Os, Ru, V, Mo (X) (Q), Nb (X) (Q), Ti (X) (Q), V (X) (Q), or Z (X) (Q), wherein X and Q are independently selected from hydrogen, halogen, alkyl group having 1-12 carbon atoms, perchlorate (ClO)₄ ^-) Tetrafluoroborate (BF)₄ ^-) hexafluoro-Phosphorus (PF)₆ ^-) Hexafluoroarsenate (AsF)₆ ^-) Hexafluoroantimonate (SbF)₆ ^-) Acetate (CH)₃COO^-) Methyl ethyl sulfonate (CH)₃(C₆H₄)SO₃ ^-) Triflate (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) Tris (ethylsulfonyl trifluoride) methane ((CF)₃SO₂)₃C^-) Or a substance having the formula: cation(s)₁-anions₁Cation, cation₁-a bridging structure₁-anions₁Cation, cation₁-a bridging structure₁-anions₁-a bridging structure₂-cations₂An anion of₂-a bridging structure₂-cations₁-a bridging structure₁-anions₁(ii) a Wherein the cation is₁-anions₁Represents a charge transfer complex; cation(s)₁And a cation₂Each represents a radical having the structure:

wherein R is₁₇And R₁₈Respectively is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 6 carbon atoms, or

R is₁₇And R₁₈Together form- (CH)₂)₂-、-(CH₂)₃-, -CH ═ CH-bridging structures, R₁₉、R₂₀、R₂₂And R₂₅Respectively represent alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen, cyano, nitro or alkoxycarbonyl with 1 to 18 carbon atomsOr R is₂₂And R₂₃And/or R₂₄And R₂₅Forming a-CH-bridging structure; r₂₆、R₂₇、R₂₈And R₂₉Each represents hydrogen, or two forms- (CH)₂)₂-、-(CH₂)₃-, -CH ═ CH-bridged structures, E₃And E₄Respectively represent O, N-CN, C (CN)₂) Or N- (aryl having 6 to 10 carbon atoms), R₃₄And R₃₅Respectively represent hydrogen, alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 18 carbon atoms, halogen, cyano, nitro, alkoxycarbonyl with 1 to 18 carbon atoms or aryl with 6 to 10 carbon atoms, R₃₀And R₃₁Each independently represents hydrogen, alkyl having 1 to 6 carbon atoms, or R₃₀And R₂₆And/or R₃₁And R₂₇Forming a-CH-bridging structure; e₁And E₂Respectively represent O, S, NR₃₆、C(R₃₆)₂Or E is₁And E₂co-form-N- (CH)₂)₂-an N-bridged structure; r₃₆Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms; z₁Represents a direct bond, -CH ═ CH-, -C (CH)₃)＝CH-、-C(CN)＝CH-、-CCl＝CCl-、-C(OH)＝CH-、-CCl＝CH-、-C≡C-、-CH＝N-N＝CH-、-C(CH₃)＝N-N＝C(CH₃) -or-CCl ═ N — N ═ CCl —; z₂Represents- (CH)₂) r or-CH₂-C₆H₄-CH₂-；r＝1～10；C^-Selected from bis (trifluoromethylsulfonyl) imide ((CF3 SO)₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) Tris (ethylsulfonyl trifluoride) methane ((CF)₃SO₂)₃C^-)；D^-Selected from halogen anion and perchlorate (ClO)₄ ^-) Tetrafluoroborate (BF)₄ ^-) hexafluoro-Phosphorus (PF)₆ ^-) Hexafluoroarsenate (AsF)₆ ^-) Hexafluoroantimonate (SbF)₆ ^-) Acetate (CH)₃COO^-) Methyl ethyl sulfonate (CH)₃(C₆H₄)SO₃ ^-) Triflate (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) Tris (ethylsulfonyl trifluoride) methane ((CF)₃SO₂)₃C^-) Wherein the bond formed with the bridging structural unit is via the radical R₁₇～R₃₆By a radical in which the radical mentioned here represents a direct bond, wherein the anion is₁And anions₂Each represents a radical having the structure:

or anions₁And anions₂Respectively represent metal salts containing titanium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), zinc (II), antimony (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II) or europium (II); r₃₇～R₄₃Respectively represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms; r₄₁～R₄₃And may also represent hydrogen; r₄₄～R₅₀Respectively represent hydrogen, alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 18 carbon atoms, halogen, cyano, alkoxycarbonyl with 1 to 18 carbon atoms or alkoxycarbonyl with 6 to 10 carbon atomsAryl of (A), R₄₈And R₄₉May also represent a benzo-fused aromatic or aromatic-like five-or six-membered heterocycle; r₅₀And also N (R)₅₁)(R₅₂)，R₄₄And R₄₅And/or R₄₆And R₄₇Form- (CH)₂)₃-、-(CH₂)₄-、-(CH₂)₅-or-CH-bridging structure; z₃Represents a direct bond, -CH-or-N-bridged structure, Z₄Represents a direct double bond, ═ CH-or ═ N-N ═ bridged structure, E₃And E₄O, S, NR respectively₅₁、C(R₅₁)(R₅₂) C ═ O or SO₂，E₅～E₈Respectively represent S, Se or NR₅₁，R₅₁And R₅₂Respectively represent an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an alkyl group having 6 to 10 carbon atoms, R₅₃～R₆₀Respectively represent hydrogen, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 18 carbon atoms, cyano, alkoxycarbonyl with 1 to 18 carbon atoms or aryl with 6 to 10 carbon atoms, or R₅₃And R₅₄And/or R₅₉And R₆₀Respectively form together- (CH)₂)₃-、-(CH₂)₄Or a-CH-bridging structure, V is 0-10, wherein the bridging structure is bridged with a bridging structural unit₁And a bridging structure₂The bond formed is via the radical R₃₇～R₅₄Is effected by a free radical of (A), or R₆₀And the radicals mentioned here represent direct bonds, bridged structures₁And a bridging structure₂Respectively represent a molecular formula of- (CH)₂) n-or- (Y)₁)s(CH₂)m-(Y₂)o-(CH₂)p-(Y₃) q-is optionally bridged with an alkoxy group having 1 to 18 carbon atoms, a halogen or a phenyl group, Y₁～Y₃O, S, NR respectively₆₁COO, CONH, NHCONH, cyclopentadienyl, cyclohexadienyl, phenyleneMesityl, naphthylene, beta-dicarbonyl, R₆₁Represents an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms, n is 0 to 12, m is 0 to 8, p is 0 to 12, o is 0 to 6, q is 0 to 1, and s is 0 to 1.

2. A compound having the formula of claim 1, for use in an electrochromic device.

3. A compound wherein the bifunctional redox dye comprising such compound has the following formula:

[ cation ]₁][M]

Wherein M represents a metal salt containing titanium (III), vanadium (IV), iron (II), cobalt (II), copper (I), silver (I), indium (I), zinc (II), antimony (III), cerium (III), samarium (II), dysprosium (II), ytterbium (II) or europium (II), wherein the cation is₁Represents a ligand having the structure:

wherein R is₁₇And R₁₈Respectively represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R₁₇And R₁₈Together form- (CH)₂)₂-、-(CH₂)₃-, or-CH ═ CH-, R₁₉、R₂₀And R₂₂～R₂₅Respectively represent hydrogen, alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 18 carbon atoms, halogen, cyano, nitro or alkoxycarbonyl with 1 to 18 carbon atoms, or R₂₂And R₂₃And/orR₂₄/R₂₅Forming a-CH-bridging structure; r₂₆、R₂₇、R₂₈And R₂₉Each represents hydrogen, or two forms- (CH)₂)₂-、-(CH₂)₃-, or-CH ═ CH-bridged structures, E₃And E₄Respectively represent O, N-CH, C (CN)₂Or N- (aryl having 6 to 10 carbon atoms), R₃₄And R₃₅Respectively represent hydrogen, alkyl with 1 to 18 carbon atoms, alkoxy with 1 to 18 carbon atoms, cyano, nitro, aryl with 1 to 18 carbon atoms and alkoxycarbonyl which can have 6 to 10 carbon atoms, or R₃₀～R₃₃Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, or R₃₀And R₂₆And/or R₃₁And R₂₇Form a-CH-bridged structure, E₁And E₂Respectively represent O, S, NR₃₆Or C (R)₃₆)₂Or E is₁And E₂co-form-N- (CH)₂)₂-N-bridged structure, R₃₆Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an aryl group having 6 to 10 carbon atoms, Z₁Represents a direct bond, -CH ═ CH-, -C (CH)₃) CH-, -C (cn) ═ CH-, -CCl ═ CCl-, -C (oh) ═ CH-, -CCl ═ CH-, -C ≡ C-, -CH ═ N ═ CH-, -C (CH3) ═ N-N ═ C (CH3) -or-CCl ═ N-N ═ CCl-, Z ═ CH ═ C ═ N ═ CCl-, and Z ═ CH ═ C (CH3 ═ and/or₂Represents- (CH)₂) Y-or-CH₂-C₆H₄-CH₂-，Y＝1～10，C^-Selected from bis (trifluoromethylsulfonyl) imide ((CF3 SO)₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) Tris (ethylsulfonyl trifluoride) methane ((CF)₃SO₂)₃C^-)；D^-Selected from halogen anion and perchlorate (ClO)₄ ^-) Tetrafluoroborate (BF)₄ ^-) hexafluoro-Phosphorus (PF)₆ ^-) Hexafluoroarsenate (AsF)₆ ^-) Hexafluoroantimonate (SbF)₆ ^-) Acetate (CH)₃COO^-) Methyl ethyl sulfonate (CH)₃(C₆H₄)SO₃ ^-) Triflate (CF)₃SO₃ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluorinated ethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) Tris (ethylsulfonyl trifluoride) methane ((CF)₃SO₂)₃C^-)。

4. A compound having the formula of claim 3, for use in an electrochromic device.

5. A method of filling an empty electro-optic device with a fluid containing a thermionic liquid electrolyte solution, wherein the electro-optic device comprises plates that are spaced apart from each other but in close proximity, each plate having an inwardly directed electrically conductive surface, the periphery of the plates being sealed by a sealing material that seals off the surface of each plate, the method comprising:

a small hole is formed in the seal of the empty device;

placing the empty device together with a container containing an ionic liquid electrolyte solution into a compartment;

drawing air out of the compartment;

submerging the empty device into the liquid so that the opening in the seal is below the surface of the liquid;

heating a portion of the liquid to at least 40 ℃;

exposing the liquid to a pressure of gas greater than the pressure inside the empty device, thereby filling the device with hot liquid;

the opening in the perimeter seal of the device is closed.