TW202348773A - Electrochromic devices and compositions including anodic component anions - Google Patents

Abstract

The present invention relates to electrochromic devices and compositions, in which the anodic component thereof includes an anodic component anion selected from at least one anodic component anion represented by the following Formulas (I) or (II), With reference to Formulas (I) and (II), R ¹and R ²are each independently selected from divalent linear or branched alkane linking group. With reference to Formula (II), R ³is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. The present invention also relates to salts including an anion represented by Formula (II). The present invention further relates to a neutral compound corresponding to Formula (II), in which hydrogen (H) is bonded to the nitrogen anion.

Description

Electrochromic devices and compositions including anions as anode components

Related applications

This application has and claims priority to U.S. Provisional Patent Application No. 63/333,182 filed on April 21, 2022 and U.S. Non-Provisional Patent Application No. 18/133,559 filed on April 12, 2023, and its disclosure The content is incorporated by reference in its entirety in each case. Field of invention

The present invention relates to electrochromic devices and compositions that include an anode component, wherein the anion is covalently bonded to the anode component or group.

Background of the invention

Electrochromism involves a reversible change in the visible color and/or visible light transmittance of a material upon the application of an electric potential. Changes in color and/or transmittance often involve alternating cycles of oxidation and reduction charge states. Generally, materials that produce color when undergoing reduction are called cathodically colored electrochromic materials; and materials that produce color when undergoing oxidation are called anodically colored electrochromic materials.

Electrochromic devices typically include opposing electrodes (eg, anode and cathode) with an electrochromic layer consisting of a solution or gel interposed therebetween. The dynamics of such electrochromic devices are typically controlled primarily by mass transport of cathode and anode components across and through the electrochromic layer. For the purpose of charge conversion, the currents in the two electrodes must be equal. If a component (cathode or anode component) moves more slowly or is transported through or across the electrochromic layer, a higher concentration of that component and, more specifically, slower movement at the electrode interface is required/ Transports higher concentration gradients of components (higher interfacial concentrations) to equalize diffusion fluxes and maintain a given current. Adjusting and/or maintaining higher concentrations of components with reduced mass delivery may require additional preparation and/or manufacturing steps and may introduce unintentional compounding errors. In some cases, mass transport imbalances can cause reduced durability of electrochromic devices, particularly when the more slowly mass transported active component experiences excessive oxidation or excessive reduction at a particular electrode.

Factors that contribute to reduced mass transport of a component and, accordingly, an imbalance in mass transport between components include (but are not limited to) reduced solubility of the component in the electrochromic layer and/or lack thereof associated therewith. of charge. In some electrochromic devices, the cathode component has a positive charge and has a counter anion associated therewith, while the anode component has no charge associated therewith. The lack of charge associated with the anode component can contribute to an undesirable mass transport imbalance associated with the cathode component.

There is a need to develop novel electrochromic devices and compositions in which the active components and, in particular, the cathode and anode components provide an improved mass transport balance. There is also a need for such newly developed electrochromic devices and compositions to provide or otherwise have improved durability, reduced manufacturing and/or operating costs, and/or improved operating efficiency associated therewith.

Summary of the invention

According to the present invention, an electrochromic device is provided, which includes: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer , wherein the first transparent electrode layer and the second transparent electrode layer are spaced apart from each other; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent conductive electrode layer . The electrochromic layer includes: (i) a cathode component; and (ii) an anode component comprising at least one anode component anion selected from the group consisting of at least one anode component anion represented by the following formula (I) or formula (II), (I) (II) Referring to formula (I), R ¹ is selected from divalent linear or branched chain alkane linking groups. Referring to formula (II), R ² is selected from a divalent linear or branched chain alkane linking group, and R ³ is selected from fluorine, a linear or branched chain fluorinated alkyl group, or a linear or branched chain perfluorinated alkyl group. base. The electrochromic layer further includes: (iii) an optional electrolyte; and (iv) a polymer matrix.

According to the present invention, an electrochromic composition is also provided, which includes: (i) a cathode component; (ii) an anode component, which includes at least one selected from the group consisting of formula (I) or formula (II) as described above. ) represents an anode component anion; (iii) an optional electrolyte; (iv) a polymeric thickener; and (v) a solvent.

Also according to the present invention, there is provided a compound represented by the following formula (IIa), (IIa) Referring to formula (IIa), R ² is selected from a divalent linear or branched chain alkane linking group; and R ³ is selected from fluorine, a linear or branched chain fluorinated alkyl group, or a linear or branched chain full chain alkyl group. Fluorinated alkyl.

According to the present invention, there is also provided a salt comprising an anion represented by the following formula (II), (II) Referring to formula (II), R ² is selected from a divalent linear or branched chain alkane linking group; and R ³ is selected from fluorine, a linear or branched chain fluorinated alkyl group, or a linear or branched chain full chain alkyl group. Fluorinated alkyl.

The features and particularities characterizing the invention are pointed out in the patent claim, which is ancillary to and forms a part of this disclosure. These and other features of the invention, its operational advantages and the specific objects attained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are illustrated and described.

Detailed description of preferred embodiments

As used herein, the articles "a", "an" and "the" include plural referents unless otherwise expressly and affirmatively limited to one referent.

Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or subratios contained therein. For example, a stated range or ratio "1 to 10" shall be deemed to include any and all values therein (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), and A subrange between the minimum value of 1 and the maximum value of 10 (and inclusive); that is, all subranges or subratios that begin with a minimum value of 1 or greater and end with a maximum value of 10 or less , such as (but not limited to) 1 to 6.1, 3.5 to 7.8 and 5.5 to 10.

Unless otherwise indicated, as used herein, a left-to-right representation of a linking group, such as a divalent linking group, includes other appropriate orientations, such as (but not limited to) right-to-left orientation. For non-limiting purposes, divalent linking groups are represented from left to right. or equivalent -C(O)O- including its right-to-left representation or equivalently -O(O)C- or -OC(O)-.

Except as indicated in operating examples or otherwise, all numbers expressing amounts of ingredients, reaction conditions, etc. used in this specification and the patent claims shall be understood to be modified in all cases by the term "about."

As used herein, molecular weight values of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.

As used herein, the polydispersity index (PDI) value represents the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of a polymer (ie, Mw/Mn).

As used herein, the term "polymer" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and graft polymers.

As used herein, the term "(meth)acrylate" and similar terms, such as "(meth)acrylic acid ester" means methacrylate and/or or acrylic. As used herein, the term "(meth)acrylic acid" means methacrylic acid and/or acrylic acid.

As used herein, the term "electrochromic" and similar terms, such as "electrochromic compound" means having an absorption spectrum that changes in response to an applied potential, at least for visible light radiation. Furthermore, as used herein, the term "electrochromic material" means any material adapted to exhibit electrochromic properties (such as adapted to have an absorption spectrum that changes in response to an applied potential, at least for visible light radiation) and includes at least one electrochromic compound.

As used herein, the term "electric potential" and related terms such as "electrical potential" means an electrical potential capable of causing a reaction in a material, such as (but not limited to) an electrochromic material Conversion from one form or state to another, as discussed in further detail herein.

As used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or timing, but rather to two different conditions or characteristics. For purposes of non-limiting illustration, the first and second states of an electrochromic compound, such as an anodically colored electrochromic compound, may vary in at least one optical property, such as (but not limited to) absorption of visible light and/or UV radiation. Different aspects. Accordingly, in accordance with various non-limiting examples disclosed herein, the anodically colored electrochromic compounds of the present invention may have different absorption spectra in each of the first and second states. By way of example, and not limitation herein, the anodically colored electrochromic compound may be transparent in a first state and tinted in a second state. Alternatively, the anodically colored electrochromic compound may have a first color in a first state and a second color in a second state.

As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs, or diagrams. Non-limiting examples of display elements include screens, monitors, and security elements, such as security tags.

As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, bezels, and optical switches.

As used herein, the term "specular" means a surface that specularly reflects a majority of incident light.

As used herein, spatial or directional terms, such as "left," "right," "inside," "outside," "above," "below," and similar terms, refer to how they are depicted in the drawings. method is used in the present invention. It is to be understood, however, that the invention may assume various alternative orientations and, therefore, such terms should not be considered limiting.

As used herein, the terms “formed over,” “deposited over,” “provided over,” “applied over,” “located over,” or “disposed over” mean that the underlying element or Formed, deposited, provided, applied, positioned or arranged on the surface of a component but not necessarily in direct (or contiguous) contact with the underlying component or the surface of the underlying component. For example, "a layer disposed over a substrate" does not exclude the presence of one or more other layers, coatings or films of the same or different composition between the disposed or formed layer and the substrate.

As used herein, the terms "interposed" and "interposed between" mean located or disposed between, but not necessarily in direct (or adjacent) contact with overlying and/or underlying elements or surfaces thereof . For example, "a layer inserted between the first substrate and the second substrate" does not exclude the presence of one or more layers having the same properties between the inserted layer and the first substrate and/or the second substrate. or other layers, coatings or films of different composition.

Unless otherwise indicated, all documents mentioned herein, such as (but not limited to) issued patents and patent applications, are deemed to be "incorporated by reference in their entirety."

As used herein, references to "linear or branched chain" groups, such as linear or branched alkyl, are to be understood herein to include: methylene or methyl; linear groups, such as linear C ₂ -C ₂₀ alkyl; and suitable branched groups, such as branched C ₃ -C ₂₀ alkyl.

As used herein, the term "alkyl" means straight or branched chain, cyclic or acyclic C ₁ -C ₂₅ alkyl. Straight chain or branched chain alkyl groups may include C ₁ -C ₂₅ alkyl groups, such as C ₁ -C ₂₀ alkyl groups, such as C ₂ -C ₁₀ alkyl groups, such as C ₁ -C ₁₂ alkyl groups, such as C ₁ -C ₆ alkyl. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, the alkyl groups further described herein. Alkyl groups may include "cycloalkyl". As used herein, the term "cycloalkyl" means a suitable cyclic group such as, but not limited to, C ₃ -C ₁₂ cycloalkyl (including, but not limited to, cyclic C ₃ -C ₁₀ alkyl , or cyclic C ₅ -C ₇ alkyl). Examples of cycloalkyl groups include, but are not limited to, those further described herein. As used herein, the term "cycloalkyl" also includes: bridged cyclic polycyclic alkyl (or bridged cyclic polycyclic alkyl), such as (but not limited to) bicyclo[2.2.1]heptyl (or norbicyclo[2.2.2]octyl; and fused-ring polycyclic alkyl (or fused-ring polycyclic alkyl), such as (but not limited to) octahydro-1H-indenyl and decahydronaphthyl .

As used herein, the term "heterocycloalkyl" means a group that is suitably cyclic and has at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. , such as (but not limited to) C ₂ -C ₁₂ heterocycloalkyl, such as C ₂ -C ₁₀ heterocycloalkyl, such as C ₅ -C ₇ heterocycloalkyl. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes: bridged ring polycyclic heterocycloalkyl, such as (but not limited to) 7-oxabicyclo[2.2.1]heptyl; and fused ring polycyclic heterocycloalkyl. Cycloheterocycloalkyl, such as (but not limited to) octahydrocyclopenta[b]pyranyl and octahydro-1H-isotrimethenyl.

The descriptions, categories and examples provided herein for alkyl, cycloalkyl, heterocycloalkyl, haloalkyl and the like also apply to alkane groups, cycloalkane groups, heterocycloalkyl groups, haloalkyl groups groups, etc., such as (but not limited to) multivalent alkane groups, such as multivalent alkane linking groups, such as divalent alkane linking groups.

As used herein, the term "aryl" and related terms, such as "aryl group" mean an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term "aromatic" and related terms, such as "aromatic group" means a cyclic structure having a stability (due to delocalization of pi electrons) that is significantly greater than the assumed localized structure. Conjugated hydrocarbons. Examples of aryl groups include C ₆ -C ₁₄ aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

As used herein, the term "heteroaryl" includes, but is not limited to, C ₃ -C ₁₈ heteroaryl, such as, but is not limited to, C ₃ -C ₁₀ heteroaryl (including fused ring polycyclic heteroaryl ) and means an aryl group having at least one heteroatom in at least one aromatic ring, in an aromatic ring or in the case of a fused-ring polycyclic heteroaryl group. Examples of heteroaryl groups include, but are not limited to, furyl, piperanyl, pyridyl, quinolyl, isoquinolyl, and pyrimidinyl.

Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl base, octyl, nonyl and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

As used herein, the term "nitrogen-containing heterocycle," such as "nitrogen-containing heterocyclic group" or "nitrogen-containing heterocyclic substituent" includes, but is not limited to, nitrogen-containing rings, wherein the nitrogen-containing heterocyclic ring The ring system is bonded through the ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amine groups (or cycloaliphatic amine groups), such as N-pyridinyl, N-hexahydropyridinyl, N-pyrrolidinyl, and decahydro isoquinolinyl; and heteroaromatic compounds such as imidazole, pyrrole, indole and carbazole.

As used herein, the reference to a "substituted" group means a group in which at least one hydrogen has been replaced or substituted by a group other than hydrogen or a "substituent," including (but not limited to) alkyl, Cycloalkyl, heterocycloalkyl, aryl and/or heteroaryl, the group or substituent is such as (but not limited to): alkoxy; halo (for example, F, Cl, I and Br); Hydroxyl; thiol group; alkylthio group; arylthio group; ketone group; aldehyde group; carboxylate group; carboxylate group; phosphate group; phosphate group; sulfonate group; sulfonate group; nitro group; cyanide group Alkyl; Alkenyl; Alkynyl; Haloalkyl; Perhaloalkyl; Heterocycloalkyl; Aryl (including alkaryl, including aryl substituted with hydroxyl, such as phenol, and including polyfused rings Aryl); aralkyl; heteroaryl (including polyfused ring heteroaryl); amine group, such as -N(R ^{11 '} ) (R ^{12 '} ), where R ^{11 '} and R ^{12 '} are each independent is selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl or heteroaryl; carboxylate group; siloxane group; alkoxysilane group; polysiloxane group; amide group; amine hydroxyformate group; carbonate group; ureido group; trialkylsilyl group; nitrogen-containing heterocycle; or combinations thereof, including classes and examples as further described herein. According to some embodiments of the present invention, substituents of substituted groups are more specifically described.

As used herein, the term "halo" and related terms, such as "halo group", "halo substituent", "halogen group" and "halogen substituent" mean a single bonded halogen group, Such as -F, -Cl, -Br and -I.

As used herein, the recitation of "substituted with halo" and related terms such as (but not limited to) haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and haloheteroaryl means at least one of And up to and including all available hydrogen groups substituted by halo groups such as, but not limited to, F, Cl or Br. The term "substituted with halo" includes "substituted with perhalo." As used herein, the term perhalo-substituted groups and related terms such as, but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl, or perhaloheteroaryl ) means a group in which all available hydrogen groups are substituted by halo groups. For purposes of non-limiting illustration: perhalomethyl- _CX3 ; and perhalophenyl- _C6X5 , where X represents one or _more halo groups such as (but not limited to) F, Cl, Br or i.

As used herein, "at least one of" is synonymous with "one or more of" whether the elements are enumerated collectively or individually. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any of A, B, or C, or A, B, or Any combination of any two or more of C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all A, B, and C.

As used herein, "selected from" is synonymous with "selected from," whether the elements are enumerated collectively or individually. Furthermore, the phrases "selected from A, B and C" and "selected from A, B or C" each mean any one of A, B or C, or any two or more of A, B or C. Any combination of more. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all A, B, and C.

The discussion of the invention herein may describe certain characteristics as "particular" or "preferred" within certain limitations (e.g., "better," "better," or "even better" within certain limitations ). It is to be understood that the present invention is not limited to or limited by such specific or preferred limitations, but encompasses the full scope of the present disclosure.

As used herein and according to some embodiments, the term "ketone", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "ketone group" and "ketone substitution" "Group" includes substances represented by -C(O)R, where R is selected from groups other than hydrogen as described below.

As used herein and according to some embodiments, the term "carboxylic acid", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "carboxylic acid group" and "carboxylic acid group" "Acid substituents" include those represented by -C(O)OH.

As used herein and according to some embodiments, the term "ester", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "ester group" and "ester substituent" ” means a formate group represented by -C(O)OR, where R is selected from groups other than hydrogen as described below.

As used herein and according to some embodiments, the term "carboxylate", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "formate group" and "Formate substituent" includes those represented by -OC(O)R, where R is selected from groups as described below.

As used herein and according to some embodiments, the term "amide", such as with respect to the groups and substituents of various groups of the compounds and components of the present invention, and related terms, such as "amide group" and "amide group" Amine substituents include those represented by -C(O)N(R)(R) or -N(R)C(O)R, where each R is independently selected from groups as described below.

As used herein and according to some embodiments, the term "carbonate", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "carbonate group" and "carbonate group" "Ester substituents" include those represented by -OC(O)OR, wherein R is selected from groups other than hydrogen as described below.

As used herein and according to some embodiments, the term "urethane", such as with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms, such as "urethane" "Ester" and "urethane substituents" include substances represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R in each case is independently is selected from groups other than hydrogen as described below.

As used herein and according to some embodiments, the term "urea", such as with respect to the groups and substituents of various groups of the compounds and components of the present invention, and related terms, such as "urea group" and "urea substituent" ” includes substances represented by -N(R)C(O)N(R)(R), where each R is independently selected from groups as described below.

As used herein and according to some embodiments, the term "silyloxy", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "silanoxy group" and "Siloxy substituents" include those represented by -O-Si(R) ₃ , wherein each R is independently selected from groups other than hydrogen as described below.

As used herein and according to some embodiments, the term "alkoxysilane", such as with respect to the groups and substituents of various groups of the compounds and components of the present invention, and related terms, such as "alkoxysilane group" and "alkoxysilane substituent" includes substances represented by -Si(OR'') _w (R), where w is 1 to 3 and t is 0 to 2, with the proviso that the sum of w and t is 3; for Each w, R'' is independently selected from an alkyl group; and for each t, R is independently selected from a group other than hydrogen as described below.

As used herein and according to some embodiments, the term "polysiloxane", such as with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms, such as "polysiloxane""Group" and "polysiloxane substituent" include substances represented by the following formula (A): (A)

Reference formula (A): t' is greater than or equal to 2, such as 2 to 200; for each t', R ^f and R ^g are each independently selected from the group R other than hydrogen as described below; and R ^h is independently the group R as described below.

Unless otherwise stated, in the above ketone, ester (carboxylate), carboxylate, amide, carbonate, urethane, urea, siloxane, alkoxysilane group and polysiloxane group Each R group in each case is independently selected from the group consisting of hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and combinations thereof ( including their categories and instances as previously described herein).

In some embodiments, reference herein to the relative ion of a component (such as the relative cation and/or the relative anion) means when the component is relative to the electrochromic layer and/or electrochromic composition of the present invention. The relative ions of the components when prepared alone and/or before being combined with the electrochromic layer and/or electrochromic composition of the present invention.

According to the present invention, the electrochromic material (of the electrochromic layer of the electrochromic device) includes an anode component, wherein the anode component includes at least one selected from the group consisting of formula (I) or formula (II) as provided above represents the anode component anion of the anode component anion. The anode component anion can be described as including an anode moiety (group or moiety), such as a ( 10H -phenanthiol-10-yl) moiety, and an anion covalently bonded to the anode moiety, such as a sulfonate anion or a trifluoride anion. methanesulfonamide anion. In some other embodiments, the anion of the anion of the anode component is covalently bonded to the anode group or moiety via a divalent linear or branched alkane linker. In some other embodiments, the anode component anion is an anodically colored electrochromic compound or group having an anion covalently bonded thereto.

According to some embodiments of the present invention and with reference to the anode component anion represented by formula (I), R ¹ is selected from divalent linear or branched C ₁ -C ₁₀ alkane linking groups.

In some embodiments and with reference to the anode component anion represented by formula (II), R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, linear Chain or branched chain C ₁ -C ₁₀ fluorinated alkyl group or straight chain or branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

With reference to the anode component anion represented by formula (I) and according to some embodiments, R ¹ is selected from divalent straight chain or branched chain C ₁ -C ₅ alkyl groups. In some embodiments, R ¹ is selected from divalent methane, divalent ethane, divalent linear or branched chain propane, divalent linear or branched chain butane, and divalent linear or branched chain pentane.

With reference to the anode component anion represented by formula (II) and according to some embodiments, R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched chain Chain C ₁ -C ₅ perfluoroalkyl. In some embodiments, ^R2 is selected from divalent methane, divalent ethane, divalent linear or branched chain propane, divalent linear or branched chain butane, and divalent linear or branched chain pentane. In some other embodiments, ^R3 is selected from fluorinated or perfluorinated versions of methyl, ethyl, linear or branched propyl, linear or branched butyl, and linear or branched pentyl, or derivative.

In some embodiments of the present invention, the anode component anion (having an anion covalently bonded thereto) can be prepared according to the non-limiting synthetic instructions further provided in the examples herein, such as by formula (I) and formula ( II) representation.

According to some other embodiments, the anode component including anions of the anode component further includes counter cations. Classes and examples of cations from which each counter cation may be independently selected include, but are not limited to: alkali metal cations such as lithium cations (Li ⁺ ), sodium cations (Na ⁺ ), and potassium cations (K ⁺ ); alkaline earth metals Cations, such as Mg ²⁺ , Ca ²⁺ and Ba ²⁺ ; optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cations, such as optionally substituted N,N-disubstituted pyrrolidinium cations , optionally substituted N,N-disubstituted piperidinium cation and optionally substituted N,N-disubstituted morpholinium cation; optionally substituted nitrogen-containing aromatic Heterocyclic ammonium cations such as optionally substituted N-substituted pyridinium cations, optionally substituted N-substituted quinolinium cations and optionally substituted N-substituted isoquinols linium cations; and tetrasubstituted ammonium cations described in further detail below. Optional substituents of the classes and examples of ammonium cations may be selected from the classes and examples of substituents previously described herein, such as, but not limited to, linear or branched alkyl, cycloalkyl, and aryl. The N-substituted and N,N-disubstituted groups of the ammonium cation may be selected from the categories and examples of substituents previously described herein, such as (but not limited to) linear or branched chain alkyl, cycloalkyl and aryl groups.

In some embodiments, the countercation of the anode component is monocationic. According to some other embodiments, the counter cation of the anode component is selected from a tetrasubstituted ammonium cation represented by the following formula (B), formula (B)

Referring to formula (B), R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted Aryl and substituted aryl. With further reference to formula (B), R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, Substituted C ₃ -C ₇ cycloalkyl, unsubstituted phenyl and substituted phenyl. In each case, the substituents for substituted cycloalkyl and substituted phenyl may be independently selected from substituents previously described herein, such as, but not limited to, straight or branched chain alkyl, cycloalkyl and aryl groups.

In some embodiments and with reference to Formula (B), each of R ^a , R ^b , R ^c and R ^d is independently selected from linear or branched chain alkyl. In some other embodiments, each of R ^a , R ^b , R ^c and R ^d of Formula (B) is independently selected from linear or branched C ₁ -C ₁₀ alkyl groups.

In some embodiments, each counter cation of the anode component is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations. In some other embodiments, each counter cation of the anode component is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations.

In some embodiments, the anode component consists of or consists of: an anode component anion selected from at least one anode component anion represented by Formula (I) or Formula (II); and a counter cation, The anode component has equal numbers of anions and counter cations and correspondingly has a neutral charge.

In some embodiments, the anode component anions are present in the electrochromic layer in an amount from 0.25 to 6.25 weight percent, or from 0.5 to 5 weight percent, or from 1 to 3 weight percent, in each case Below, the weight percentage is based on the total weight of the electrochromic layer.

According to some embodiments, the anode component of the electrochromic layer includes one or more other anodes in addition to the anode component having a covalently bonded anion, such as represented by Formula (I) and/or Formula (II). Electrochromic compounds such as (but not limited to): ferrocene and/or ferrocene derivatives in which at least one cyclopentadienyl ring is substituted with at least one substituent (including the substituents previously described herein) ); 5,10-dihydro-5,10-bis (linear or branched chain C ₁ -C ₁₀ alkyl) phenanthrene, such as 5,10-dihydro-5,10-dimethylphenanthrene; N -Substituted phenanthrenes, such as N-phenylphenanthrenes; and combinations thereof. In some embodiments, the other anodic electrochromic component is present in an amount from 1 to 50 weight percent, from 1 to 25 weight percent, or from 1 to 10 weight percent, or from 1 to 5 weight percent. , the weight percentages are each based on the total weight of the anionic component of the anode and other anode electrochromic components. According to some embodiments, when another anode component is present (in addition to the anode component anion having a covalently bonded anion), another cathode component (or other suitable amount of cathode component) may also be present. In some embodiments, other cathode components include one or more cathode components represented by formulas (III) and/or (IV).

In some embodiments, the cathode component of the electrochromic layer of the electrochromic device includes at least one of the following: 1,1'-disubstituted 4,4'-dipyridine represented by the following formula (III) onium cation, or 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted 4,4'-dipyridinium) cation represented by the following formula (VI): Formula (III) ) Formula (IV)

Referring to formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl.

Referring to formula (IV) and according to some embodiments, R ⁶ and R ⁸ are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and R ⁷ is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group.

The aryl groups in the unsubstituted aryl groups and substituted aryl groups of R ⁴ and R ⁵ of formula (III) and R ⁶ and R ⁸ of formula (IV) from which each can be independently selected include as previously described herein Recited aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl and anthracenyl. The cycloalkyl groups in the unsubstituted cycloalkyl group and the substituted cycloalkyl group of R ⁴ and R ⁵ of the formula (III) and R ⁶ and R ⁸ of the formula (IV), which can be each independently selected, include as follows: Cycloalkyl groups previously described herein include, but are not limited to, cyclopentyl, cyclohexyl and cycloheptyl.

Substituents in the substituted cycloalkyl and substituted aryl groups of R ⁴ and R ⁵ of formula (III) and R ⁶ and R ⁸ of formula (IV) from which each can be independently selected include as previously described herein Describe the substituents. In some embodiments, each of the substituted cycloalkyl and substituted aryl groups of R ⁴ and R ⁵ of Formula (III) and R ⁶ and R ⁸ of Formula (IV) can be independently selected therein. The substituents are each independently selected from: alkoxy; halo (for example, F, Cl, I and Br); hydroxyl; thiol; alkylthio; arylthio; ketone; aldehyde; haloalkyl radical; perhaloalkyl; heterocycloalkyl; aryl; aralkyl (such as benzyl); heteroaryl; and amine.

Linear or branched chain alkyl groups from which R ⁴ and R ⁵ of formula (III) and R ⁶ and R ⁸ of formula (IV) may each be independently selected include classes and examples of alkyl groups as previously described herein, Such as (but not limited to) methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, linear or branched hexyl, and linear or branched heptyl .

With further reference to formula (III) and according to some embodiments of the present invention, R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl. base.

With further reference to formula (IV) and according to some embodiments of the present invention, R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl. group, and R ⁷ is selected from a divalent linear or branched C ₁ -C ₈ alkane linking group. In some other embodiments, R ⁷ of formula (IV) is a divalent linear or branched C ₁ -C ₅ alkane linking group, such as a divalent linear or branched C ₃ -C ₅ alkane linking group.

According to some embodiments of the invention, the cathode component further includes a counter anion. In some other embodiments, the cathode component includes equal numbers of cations and counter anions (or anions) and accordingly, the cathode component has a net neutral charge. In some embodiments, each counter anion of the cathode component is independently selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- or B(phenyl) ₄ ^- . In some embodiments, the relative anion of the cathode component does not include and is not selected from anions such as the anode component represented by formulas (I) and (II).

According to some embodiments of the present invention, the cathode component is present in the electrochromic layer in an amount of 0.25 to 6.25 weight percent, or 0.5 to 5 weight percent, or 1 to 3 weight percent, in various In this case, the weight percentage is based on the total weight of the electrochromic layer.

In some embodiments of the invention, the electrochromic layer of the electrochromic device of the invention includes an electrolyte. In some embodiments, the electrolyte includes at least one electrolyte anion and at least one electrolyte cation. In some embodiments, the electrolyte of the electrochromic layer includes equal numbers of electrolyte anions and electrolyte cations, and accordingly has a net neutral charge.

In some embodiments, the electrolyte of the electrochromic layer includes at least one electrolyte anion, wherein each electrolyte anion is independently selected from chloride, hexafluorophosphate, and bis(perfluoro(linear or branched chain C ₁ -C ₆ Alkylsulfonyl)imine. In some other embodiments, the electrolyte of the electrochromic layer includes at least one electrolyte cation, wherein each electrolyte cation is independently selected from: sodium; potassium; lithium; ammonium cation, such as tetrakis ( Straight chain or branched chain C ₁ -C ₆ ) ammonium, and tris (C ₅ -C ₈ cycloalkyl) - (straight chain or branched chain C ₁ -C ₆ alkyl) ammonium; 1- (straight chain or branched chain) C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ -C ₆ alkyl) imidazolium; 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear Or branched chain C ₁ -C ₆ alkyl)pyrrolidinium; 1-(straight chain or branched chain C ₁ -C ₆ alkyl)-1-(straight chain or branched chain C ₁ -C ₆ alkyl) piperidine onium; or a phosphonium cation, such as (but not limited to) tetrakis (linear or branched chain C ₁ -C ₆ alkyl) phosphonium, or tris (C ₅ -C ₈ cycloalkyl) - (linear or branched chain C ₁ -C ₆ alkyl)phosphonium.

In some embodiments, the electrolyte of the electrochromic layer includes: at least one electrolyte anion, wherein each electrolyte anion is independently selected from the group consisting of bis(perfluoro(linear or branched chain C ₁ -C ₆ alkyl sulfonyl) oxide amine; and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(linear or branched chain C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ -C ₆ alkyl) Imidazolium, 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear or branched chain C ₁ -C ₆ alkyl) pyrrolidinium, or 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear or branched chain C ₁ -C ₆ alkyl)piperidinium.

In some other embodiments, the electrolyte of the electrochromic layer includes: at least one electrolyte anion, wherein each electrolyte anion is bis(trifluoromethylsulfonyl)imide; and at least one electrolyte cation, wherein each electrolyte cation is independently Selected from 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-1-butylpyrrolidinium and 1-methyl-1-propylpiper dinium.

In some embodiments, the electrolyte is present in the electrochromic layer in an amount from 1 to 75 weight percent, or from 5 to 50 weight percent, or from 10 to 30 weight percent, in each case, wt. Percentages are based on the total weight of the electrochromic layer.

According to some other embodiments, the electrochromic layer of the present invention includes a solvent. In some other embodiments, the solvent is present in the electrochromic layer instead of or along with the electrolyte. In some embodiments, the solvent may include at least one of the following: ethyl carbonate, propyl carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, Carboxylic acid esters of polyethylene glycol, cyclotenine, α,ω-(C ₂ -C ₈ ) dinitrile or bis (linear or branched chain C ₁ -C ₈ ) acetamide. Without intending to be bound by any theory, and according to some embodiments, it is believed that the solvent acts at least in part as a plasticizer within (or plasticizes) the electrochromic layer. In some embodiments, the solvent is present in the electrochromic layer in an amount of 10 to 75 weight percent, or 20 to 60 weight percent. In each case, the weight percentage is based on the total weight of the electrochromic layer and the solvent. .

The electrochromic layer of the electrochromic device of the present invention includes a polymer matrix. The polymer matrix includes at least one polymer. In some embodiments, the polymer matrix is a gelled polymer matrix, a cross-linked polymer matrix, and/or a thermoplastic polymer matrix.

In some embodiments, the polymer matrix includes a polymer, wherein the polymer includes at least one of: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co- - Perfluoro (linear or branched C ₁ -C ₆ alkylene)) or poly((linear or branched C ₁ -C ₈ alkyl) (meth)acrylate).

In some embodiments, the polymeric matrix is present in the electrochromic layer in an amount from 5 to 80 weight percent, or from 10 to 60 weight percent, or from 15 to 50 weight percent, in each case , the weight percentage is based on the total weight of the electrochromic layer.

In some embodiments, the electrochromic layer of the electrochromic device of the present invention may further include one or more optional additives recognized in the art, such as (but not limited to) thermal stabilizers, UV stabilizers, flow stabilizers, Chemical regulators, static colorants (such as static dyes and/or static dyes), kinetic additives (to promote electrode reactions) and combinations thereof. A non-limiting class of heat stabilizers recognized in the art are phenols such as 2,6-di-tertiary butylphenol and compounds including 2,6-di-tertiary butylphenol groups or moieties. A non-limiting class of UV stabilizers recognized in the art are hindered amine light stabilizers (HALS), such as 2,2,6,6-tetramethylpiperidine and including 2,2,6,6-tetramethylpiperdine. Compounds containing piperidine groups or moieties. Static colorants include colorants whose absorption spectrum does not change in response to actinic radiation (such as UV and/or visible light) or applied electrical potential, and excludes photochromic compounds and electrochromic compounds. Non-limiting classes of kinetic additives include salts such as alkali and alkaline earth metal salts of perchlorate, tetrafluoroborate and hexafluorophosphate; and tetraalkylammonium salts. Non-limiting examples of rheology modifiers include: dialkoxyacetophenones, such as 3',4'-dimethoxyacetophenone; and optionally substituted cycloalkyl aryl ketones, such as 1-Hydroxycyclohexylphenylketone. Each optional additive may be present in any suitable active amount, such as 0.05 to 5 weight percent, based on the total solids weight of the electrochromic layer (including the weight of the optional additives).

The electrochromic layer of the electrochromic device of the present invention may have any suitable thickness. In some embodiments, the electrochromic layer has a thickness of 50 microns to 800 microns.

For the purpose of non-limiting illustration, an electrochromic device (3) according to the invention is depicted in Figure 1. The electrochromic device (3) includes a first substrate (11) having a first surface (14) and a second surface (17). The first surface (14) of the first substrate (11) includes a conductive first transparent electrode layer (20). The first transparent electrode layer (20) is located on at least a portion of the first surface (14) of the first substrate (11). In some embodiments, the first transparent electrode layer (20) is in the form of one or more patterns (such as one or more designs and/or logos) on the first surface (14) of the first substrate (11). In some other embodiments, the first transparent electrode layer (20) forms a substantially continuous layer on the first surface (14) of the first substrate (11). In some embodiments, the first transparent electrode layer (20) is in electrical contact with at least one first electrical conductor (21), which may be a first conductive line.

The electrochromic device (3) includes a second substrate (23) having a first surface (26) and a second surface (29). The first surface (26) of the second substrate (23) includes a conductive second transparent electrode layer (32). The second transparent electrode layer (32) is located on at least a portion of the first surface (26) of the second substrate (23). In some embodiments, the second transparent electrode layer (32) is in the form of one or more patterns (such as one or more designs and/or logos) on the first surface (26) of the second substrate (23). In some other embodiments, the second transparent electrode layer (32) forms a substantially continuous layer on the first surface (26) of the second substrate (23). In some embodiments, the second transparent electrode layer (32) is in electrical contact with at least one second electrical conductor (33), which may be a second electrically conductive second wire.

Referring further to the electrochromic device (3) of Figure 1, the first transparent electrode layer (20) and the second transparent electrode layer (32) are spaced apart from each other and face each other.

The electrochromic device (3) further includes an electrochromic layer (35) interposed between the first transparent electrode layer (20) and the second transparent electrode layer (32). In some embodiments, the electrochromic layer (35) is interposed between the first transparent electrode layer (20) and the second transparent electrode layer (32) and is in contact with the first transparent electrode layer and the second transparent electrode layer. Adjacency relationship.

In some embodiments, the first substrate and the second substrate of the electrochromic device of the present invention are each independently selected from transparent substrates. In some embodiments, the transparent substrate from which the first and second substrates may be independently selected is made of materials including, but not limited to, silica glass, organic polymers such as, but not limited to ) polycarbonate polymers) and combinations thereof. In some embodiments, the transparent substrate from which the first and second substrates are each independently selectable is made of a material including silica glass. The first substrate and the second substrate may independently have any suitable thickness. In some embodiments, the first substrate and the second substrate independently have a thickness of 1 mm to 25 mm, or 2 mm to 10 mm.

In some embodiments, the first and second transparent electrode layers of the electrochromic device of the present invention include conductive inorganic oxides, conductive organic materials, conductive metals, and/or conductive carbon, such as carbon nanotubes and/or graphene. . Examples of conductive inorganic oxides include, but are not limited to, tin oxide, which may be doped with doping materials such as indium, and zinc oxide, which may further include aluminum, for example. Examples of conductive organic materials include, but are not limited to, poly(3,4-ethylenedioxythiophene), poly(4,4-dioctylcyclopentadithiophene), and poly(3,4-ethylenedioxythiophene). Thiophene): poly(styrene sulfonate). In some embodiments, the first and second transparent electrode layers may each independently be in the form of a metal wire network, a carbon nanotube network, and/or a graphene layer. In some embodiments, the first and second transparent electrode layers are each independently selected from translucent metal layers. In some other embodiments, one of the first and second transparent electrode layers includes (or has associated therewith) a reflective metal layer (including, for example, aluminum, gold, and/or silver), and the electrochromic device is reflective Electrochromic devices, such as controllable reflective mirrors.

According to some embodiments, the first and second electrode layers of the electrochromic device of the present invention each independently include a conductive material selected from the following: indium tin oxide, poly(3,4-ethylenedioxythiophene): poly (styrene sulfonate) or combinations thereof.

According to some embodiments of the present invention, the first and second electrode layers of the electrochromic device may independently have any suitable thickness, provided that both are transparent and conductive. In some embodiments, the first and second electrode layers of the electrochromic device of the present invention each independently have a thickness of 0.01 micron to 10 micron.

Examples of articles, such as articles, that may include or be defined by the electrochromic devices of the present invention include (but are not limited to): energy-saving and/or security transparent parts (or windows), such as building and transportation transparent parts. accessories or windows; mirrors, such as rearview mirrors; optical filters; and ophthalmic items, such as corrective lenses, non-corrective lenses, magnifying glasses, protective lenses and goggles; and any other light requiring variable and controllable Transmissive and/or colored articles or applications.

The present invention also relates to electrochromic compositions comprising: (i) a cathode component; (ii) an anode component comprising at least one compound of formula (I) or formula (II) as previously described herein. ) represents an anode component anion; (iii) an optional electrolyte; (iv) a polymeric thickener; and (v) a solvent.

The cathode component, the anode component including an anion of the anode component selected from at least one anode component anion represented by formula (I) or formula (II), and the optional electrolyte are each as described previously herein with respect to the electrolyte of the present invention. The electrochromic layer of the electrochromic device is described.

In some embodiments, the cathode component is present in the electrochromic composition in an amount from 0.25 to 6.25 weight percent, or from 0.5 to 5 weight percent, or from 1 to 3 weight percent, in each case Below, the weight percentage is based on the total weight of the electrochromic composition.

In some embodiments, the anode component anion is present in the electrochromic composition in an amount of 0.25 to 6.25 weight percent, or 0.5 to 5 weight percent, or 1 to 3 weight percent, in various In this case, the weight percentage is based on the total weight of the electrochromic composition.

According to some embodiments, in addition to the anode component anion having a covalently bonded anion (such as represented by Formula (I) and/or Formula (II)), the anode component of the electrochromic composition includes one or more other Anodic electrochromic compounds, such as (but not limited to): ferrocene and/or ferrocene derivatives (wherein at least one cyclopentadienyl ring is subjected to at least one substituent (including the substituents previously described herein) Substituted); 5,10-dihydro-5,10-bis (linear or branched chain C ₁ -C ₁₀ alkyl) phenanthrene, such as 5,10-dihydro-5,10-dimethylphenanthrene; N-Substituted phenanthrenes, such as N-phenylphenanthrenes; and combinations thereof. In some embodiments, the other anodic electrochromic component is present in an amount from 1 to 50 weight percent, from 1 to 25 weight percent, or from 1 to 10 weight percent, or from 1 to 5 weight percent. , the weight percentages are each based on the total weight of the anionic component of the anode and other anode electrochromic components. According to some embodiments, when another anode component is present (in addition to the anode component anion having a covalently bonded anion), another cathode component (or other suitable amount of cathode component) may also be present. In some embodiments, other cathode components include one or more cathode components represented by formulas (III) and/or (IV).

In some embodiments, the electrolyte is present in the electrochromic composition in an amount from 1 to 75 weight percent, or from 5 to 50 weight percent, or from 10 to 30 weight percent, in each case, Weight percentage is based on the total weight of the electrochromic composition.

In some embodiments, the polymeric thickener of the electrochromic composition of the electrochromic composition includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(meta)acrylonitrile Vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched chain C ₁ -C ₆ alkyl)) or poly((linear or branched chain C ₁ -C ₈ alkyl) ( meth)acrylate).

In some embodiments, the polymeric thickener is present in the electrochromic composition in an amount of 5 to 80 weight percent, or 10 to 60 weight percent, or 15 to 50 weight percent, in various In this case, the weight percentage is based on the total weight of the electrochromic composition.

The electrochromic composition of the present invention includes a solvent. In some embodiments, the solvent of the electrochromic composition includes at least one of the following: ethyl carbonate, propyl carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, Polyethylene glycol, polyethylene glycol carboxylic acid ester, cyclotenine, α,ω-(C ₂ -C ₈ ) dinitrile or bis (linear or branched chain C ₁ -C ₈ ) acetamide.

In some embodiments, the solvent is present in the electrochromic composition in an amount of 10 to 75 weight percent, or 20 to 60 weight percent, or 25 weight percent to 50 weight percent, in each case the weight percent is The total weight of the electrochromic composition.

According to some embodiments, the anode component including anions of the anode component further includes counter cations. Categories and examples of cations from which each counter cation can be independently selected include those previously described herein with respect to electrochromic devices. In some embodiments of the electrochromic composition of the present invention, each counter cation is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations. According to some other embodiments, each counter cation system is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations.

In some embodiments, the cathode component of the electrochromic composition further includes a relative anion, wherein each relative anion of the cathode component is selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- and B(phenyl) ₄ ^- . In some embodiments, the relative anion of the cathode component of the electrochromic composition does not include and is not selected from anions of the anode component such as those represented by formulas (I) and (II).

In some embodiments, the electrochromic composition of the present invention may include one or more optional additives recognized in the art, such as (but not limited to) thermal stabilizers, UV stabilizers, rheology modifiers, Static colorants (such as static dyes and/or static dyes), kinetic additives (to promote electrode reactions) and combinations thereof. In each case, optional additives are as previously described herein with respect to the electrochromic devices of the present invention. Each optional additive may be present in the electrochromic composition in any suitable active amount, such as 0.05 to 5 weight percent, based on the total weight of the electrochromic composition (including the weight of the optional additives).

According to some embodiments of the present invention, the electrochromic layer of the electrochromic device is formed from the electrochromic composition of the present invention. According to some embodiments of the present invention, the formation of the electrochromic composition and the electrochromic layer includes the following steps. First, all components of the electrochromic composition except the polymeric thickener are mixed under shear (such as using an impeller) until a homogeneous mixture is formed. Next, a polymeric thickener is added and the combination is homogenized, causing the formation of a viscous slurry. A liquid film of viscous slurry is formed on a sacrificial or temporary liner (in some embodiments, composed of polyethylene terephthalate), such as using a spatula or stretch rod. The liquid film is subjected to high temperatures (such as 60°C to 90°C) while on the sacrificial/temporary liner for 3 to 10 minutes, causing the formation of a cured film/layer, which is the electrochromic layer. The cured film/electrochromic layer is separated from the sacrificial/temporary liner (which is discarded), cut to size (if necessary) and placed over or on top of the first transparent electrode layer of the first substrate. The second transparent electrode of the second substrate is placed above or on the other (or opposite/exposed) side of the electrochromic layer to form a structure including the first substrate, the first transparent electrode, the electrochromic layer, and the A stack of two transparent electrodes and a second substrate. The stack may further include electrical connections in independent electrical contact with the first and second transparent electrodes. The stack (with optional spacers surrounding at least the outer edge of the electrochromic layer) is subjected to vacuum lamination while applying a high temperature, such as 110°C to 200°C, for a period such as 10 to 30 minutes. After cooling, the thus formed electrochromic device was removed from the vacuum lamination apparatus.

According to the invention there are also provided compounds represented by formula (IIa) as previously described herein. The R ² divalent linking group and the R ³ group of formula (IIa) are each as described previously herein with respect to formula (II) of the electrochromic device of the present invention.

In some embodiments, R ² of formula (IIa) is selected from divalent linear or branched C ₁ -C ₁₀ alkane linking groups; and R ³ of formula (IIa) is selected from fluorine, linear or branched Chain C ₁ -C ₁₀ fluorinated alkyl group or linear or branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

In some other embodiments, R ² of formula (IIa) is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ of formula (IIa) is selected from a linear or branched chain. C ₁ -C ₅ perfluoroalkyl.

In some embodiments, compounds represented by Formula (IIa) can be prepared by combining a salt of the anion represented by Formula (II), such as a sodium (Na ⁺ ) or potassium (K ⁺ ) salt with a strong acid, such as (but not limited to) ) HCl, sulfuric acid (H ₂ SO ₄ ) and bistrifluoromethanesulfonamide acid, followed by purification, separation and processing procedures recognized in the art.

According to the invention, salts comprising anions represented by formula (II) as previously described herein are also provided. The R ² divalent linking group and the R ³ group according to the present invention including the salt of the anion represented by formula (II) are each as described previously herein with respect to formula (II) of the electrochromic device of the present invention.

In some embodiments, R ² in the salt of formula (II) according to the present invention is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and the salt of the present invention is of formula (II) R ³ is selected from fluorine, linear or branched chain C ₁ -C ₁₀ fluorinated alkyl group or linear or branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

In some other embodiments, R ² in the salt of the present invention of formula (II) is selected from a divalent linear or branched chain C ₁ -C ₅ alkane linking group; and the salt of the present invention of formula (II) R ³ is selected from linear or branched chain C ₁ -C ₅ perfluorinated alkyl groups.

According to some embodiments, the salts of the present invention include: an anion represented by formula (II); and a counter cation. In some embodiments of the salts of the present invention, the number of anions and countercations are equal, and therefore the salt has a neutral charge. In some embodiments, the relative cation of the salt according to the invention is as described previously herein with respect to the relative cation of the anode component of the invention, such as (but not limited to) with reference to Formula (B).

In some embodiments, the countercation of the salt according to the present invention is selected from tetrakis (linear or branched chain alkyl) ammonium cations. In some other embodiments, the countercation of the salt according to the present invention is selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations.

The salts of the present invention may be in any suitable form, such as in solid form or in ionic liquid form. In some embodiments, the salts of the present invention are present in the form of a liquid mixture further comprising a solvent, such as water and/or an organic solvent. The organic solvent may be selected from any suitable organic solvent, such as (but not limited to) ethyl carbonate, propyl carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol Alcohol, polyethylene glycol carboxylic acid ester, cyclotenine, α,ω-(C ₂ -C ₈ ) dinitrile or bis (linear or branched chain C ₁ -C ₈ ) acetamide.

The invention may further be characterized by one or more of the following non-limiting items.

Clause 1: An electrochromic device comprising: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive layer A surface of the electrode layer, wherein the first transparent electrode layer and the second transparent electrode layer are relatively spaced and opposed; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent electrode layer; between the transparent conductive electrode layers, wherein the electrochromic layer includes, (i) a cathode component, (ii) an anode component including at least one selected from the group consisting of the following formula (I) or formula (II): anode component anion one anode component anion, (I) (II) wherein for formula (I), R ¹ is selected from a divalent straight or branched chain alkane linker, and wherein for formula (II), R ² is selected from a divalent straight or branched alkane linker. group, and R ³ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluoroalkyl, (iii) an optional electrolyte, and (iv) a polymer matrix.

Item 2: The electrochromic device of item 1, wherein for formula (I), R ¹ is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group, and wherein for formula (II) , R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, a linear or branched C ₁ -C ₁₀ fluorinated alkyl group, or a linear or branched Chain C ₁ -C ₁₀ perfluoroalkyl.

Clause 3: The electrochromic device of Clause 1 or Clause 2, wherein for formula (I), R ¹ is selected from a divalent linear or branched chain C ₁ -C ₅ alkyl group, and wherein for formula (I) II), R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched C ₁ -C ₅ perfluorinated alkyl group.

Clause 4: The electrochromic device of Clause 1, wherein the anode component further comprises a countercation.

Clause 5: The electrochromic device of Clause 4, wherein each counter cation is independently selected from the group consisting of optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cations, optionally substituted nitrogen-containing aromatic cations Heterocyclic ammonium cations, tetrasubstituted ammonium cations, or combinations thereof.

Clause 6: An electrochromic device as in Clause 4 or Clause 5, wherein each counter cation is independently selected from a tetrasubstituted ammonium cation represented by the following formula (B), Formula (B) wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl and substituted The aromatic base.

Item 7: The electrochromic device as in Item 6, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted phenyl or substituted phenyl.

Item 8: The electrochromic device of item 6 or 7, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl groups.

Clause 9: The electrochromic device of any one of clauses 4, 5, 6, 7 or 8, wherein each counter cation is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations.

Clause 10: The electrochromic device according to any one of clauses 4, 5, 6, 7, 8 or 9, wherein each relative cation is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkane base) ammonium cation.

Clause 11: The electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the cathode component comprises at least one of the following: 1,1'-disubstituted 4,4'-dipyridinium cation represented by formula (III), or 1,1-(alkane-α,ω-diyl)-bis represented by the following formula (VI) -(1'-Substituted 4,4'-bipyridinium) cation, formula (III) Formula (IV) Wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ - C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl , unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and R ⁷ is selected from divalent straight chain or Branched chain C ₁ -C ₁₀ alkane linking group.

Item 12: The electrochromic device as in Item 11, wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted benzene and substituted phenyl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl, and R ⁷ is selected from a divalent linear or branched C ₁ -C ₈ alkane linking group.

Clause 13: An electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, wherein the cathode component further comprises a counter anion, Each relative anion of the cathode component is selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- or B(phenyl) ₄ ^- .

Clause 14: An electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the electrolyte is present and contains , at least one electrolyte anion, wherein each electrolyte anion is independently selected from the group consisting of bis(perfluoro (linear or branched chain C ₁ -C ₆ alkyl sulfonyl)imines, and at least one electrolyte cation, wherein each electrolyte cation is Independently selected from 1-(linear or branched chain C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ -C ₆ alkyl) imidazolium; 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear or branched C ₁ -C ₆ alkyl)piperidinium; or a phosphonium cation such as (but not limited to) tetrakis (linear or branched C ₁ -C ₆ alkyl) base) phosphonium, or tris(C ₅ -C ₈ cycloalkyl) - (linear or branched chain C ₁ -C ₆ alkyl) phosphonium; or an ammonium cation, such as (but not limited to) tetra(linear or branched chain) C ₁ -C ₆ ) ammonium, and tris (C ₅ -C ₈ cycloalkyl)-(linear or branched chain C ₁ -C ₆ alkyl) ammonium.

Clause 15: An electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein the polymer matrix comprises Polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro (linear or branched chain C ₁ -C ₆ alkyl)) or poly((linear or branched chain C ₁ -C ₈ alkyl)(meth)acrylate).

Item 16: An article containing the electrochromic electrochromic product according to any one of Item 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 Device, wherein the article is selected from the group consisting of energy-saving transparent parts, privacy transparent parts, mirrors, optical filters, or ophthalmic articles.

Clause 17: An electrochromic composition comprising, (i) a cathode component, (ii) an anode component comprising at least one anode selected from the group consisting of the following formula (I) or formula (II) One of the component anions is the anode component anion, (I) (II) wherein for formula (I), R ¹ is selected from a divalent straight or branched chain alkane linker, and wherein for formula (II), R ² is selected from a divalent straight or branched alkane linker. group, and R ³ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluoroalkyl, (iii) an optional electrolyte, (iv) a polymeric thickener; and (iii) an optional electrolyte; v) a solvent.

Item 18: The electrochromic composition of item 17, wherein for formula (I), R ¹ is selected from a divalent linear or branched chain C ₁ -C ₁₀ alkane linking group, and wherein for formula (II) ), R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, a linear or branched C ₁ -C ₁₀ fluorinated alkyl group or a linear or Branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

Clause 19: The electrochromic composition of Clause 17 or Clause 18, for formula (I), R ¹ is selected from a divalent linear or branched chain C ₁ -C ₅ alkyl group, and wherein for formula (I) II), R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched C ₁ -C ₅ perfluorinated alkyl group.

Clause 20: The electrochromic composition according to any one of clauses 17, 18 or 19, wherein the anode component further comprises a counter cation.

Item 21: The electrochromic composition of item 20, wherein each relative cation is independently selected from optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cations, optionally substituted nitrogen-containing aromatic ammonium cations. Group heterocyclic ammonium cations, tetra-substituted ammonium cations, or combinations thereof.

Clause 22: An electrochromic composition as in Clause 20 or Clause 21, wherein each relative cation is selected from a tetrasubstituted ammonium cation represented by the following formula (B), Formula (B) wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl and substituted The aromatic base.

Item 23: The electrochromic composition as in Item 22, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted phenyl or substituted phenyl.

Item 24: The electrochromic composition of item 22 or 23, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl groups.

Item 25: The electrochromic composition according to any one of Items 17, 18, 19, 20, 21, 22, 23 or 24, wherein each relative cation is independently selected from four (linear or branched chain alkanes) base) ammonium cation.

Item 26: The electrochromic composition according to any one of Items 17, 18, 19, 20, 21, 22, 23, 24 or 25, wherein each relative cation is independently selected from four (linear or branched Chain C ₁ -C ₁₀ alkyl) ammonium cation.

Item 27: The electrochromic composition according to any one of Items 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26, wherein the cathode component includes at least one of the following: 1,1'-disubstituted 4,4'-dipyridinium cation represented by the following formula (III), or 1,1-(alkane-α,ω-diyl)- represented by the following formula (VI) Bis-(1'-substituted 4,4'-bipyridinium) cation, formula (III) Formula (IV) Wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ - C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl , unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and R ⁷ is selected from divalent straight chain or Branched chain C ₁ -C ₁₀ alkane linking group.

Item 28: The electrochromic composition as in Item 27, wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted Phenyl and substituted phenyl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl group, and R ⁷ is selected from a divalent straight chain or branched chain C ₁ -C ₈ alkane linking group.

Clause 29: The electrochromic composition according to any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28, wherein the cathode component further comprises a counter anion , wherein each relative anion of the cathode component is selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ ^C- or B(phenyl) _4- ^.

Clause 30: An electrochromic composition according to any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29, wherein the electrolyte is present and Comprising, at least one electrolyte anion, wherein each electrolyte anion is independently selected from the group consisting of bis(perfluoro (linear or branched chain C ₁ -C ₆ alkylsulfonyl)imines, and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(linear or branched chain C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ -C ₆ alkyl) imidazolium; 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear or branched chain C ₁ -C ₆ alkyl)piperidinium; or a phosphonium cation such as (but not limited to) tetrakis (linear or branched chain C ₁ -C ₆ Alkyl)phosphonium, or tris( _C5 - _C8cycloalkyl )-(linear or branched _C1 - _C6alkyl )phosphonium; or ammonium cations such as (but not limited to) tetra(linear or branched) Chain C ₁ -C ₆ ) ammonium, and tris (C ₅ -C ₈ cycloalkyl) - (linear or branched chain C ₁ -C ₆ alkyl) ammonium.

Clause 31: The electrochromic composition according to any one of Clause 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, wherein the polymerization thickens The agent includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro (linear or branched) chain C ₁ -C ₆ alkyl)) or poly(linear or branched chain C ₁ -C ₈ alkyl)(meth)acrylate).

Clause 32: The electrochromic composition according to any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or 31, wherein the solvent Contains at least one of the following: ethylene carbonate, propyl carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, and carboxylic acid esters of polyethylene glycol , cyclotetrane, α,ω-(C ₂ -C ₈ ) dinitrile or bis (linear or branched chain C ₁ -C ₈ ) acetamide.

Clause 33: A compound represented by the following formula (IIa), (IIa) wherein R ² is selected from divalent linear or branched chain alkane linking groups; and R ³ is selected from fluorine, linear or branched chain fluorinated alkyl, or linear or branched chain perfluorinated alkyl.

Item 34: The compound of item 33, wherein R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from a fluorine, linear or branched C ₁ - C ₁₀ fluorinated alkyl group or linear or branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

Clause 35: A compound as in Clause 33 or Clause 34, wherein R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched C ₁ -C ₅ perfluoroalkyl.

Clause 36: A salt containing an anion represented by formula (II) below, (II) wherein R ¹ is selected from a divalent linear or branched chain alkane linking group; and R ² is selected from fluorine, a linear or branched chain fluorinated alkyl group, or a linear or branched chain perfluorinated alkyl group.

Item 37: The salt of item 36, wherein for the anion represented by formula (II), R ² is selected from a divalent straight or branched C ₁ -C ₁₀ alkane linking group, and R ³ is selected from From fluorine, straight chain or branched chain C ₁ -C ₁₀ fluorinated alkyl group or straight chain or branched chain C ₁ -C ₁₀ perfluorinated alkyl group.

Clause 38: A salt as in Clause 36 or Clause 37, wherein for the anion represented by formula (II), R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from linear or branched chain C ₁ -C ₅ perfluorinated alkyl groups.

Clause 39: A salt according to any of Clause 36, 37 or 38, wherein the salt further comprises a counter cation.

Clause 40: The salt of clause 39, wherein each counter cation is independently selected from the group consisting of optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cations, optionally substituted nitrogen-containing aromatic heterocyclic ammonium cations cation, tetrasubstituted ammonium cation, or combinations thereof.

Clause 41: A salt as in Clause 39 or Clause 40, wherein each counter cation is selected from a tetrasubstituted ammonium cation represented by the following formula (B), Formula (B) wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl and substituted The aromatic base.

Item 42: The salt of item 41, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted phenyl or substituted phenyl.

Item 43: A salt as in item 41 or 42, wherein R ^a , R ^b , R ^c and R ^d are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl groups.

Clause 44: A salt according to any one of Clause 36, 37, 38, 39, 40, 41, 42 or 43, wherein each counter cation is independently selected from the group consisting of tetrakis (linear or branched chain alkyl) ammonium cations .

Clause 45: A salt according to any one of clauses 36, 37, 38, 39, 40, 41, 42, 43 or 44, wherein each relative cation is independently selected from four (linear or branched chain C ₁ - C ₁₀ alkyl) ammonium cation.

The invention is more particularly described in the following examples, which are intended to be illustrative only, as many modifications and variations therein will be apparent to those skilled in the art. Example

In part-1 of the following examples, the synthesis of the anionic anions of the anode components and salts according to the invention is described. In Section-2, the preparation of an electrochromic device according to the present invention is described. In Section-3, the evaluation of the electrochromic device of Section-2 is described. Part -1 Synthesis Example 1

A non-limiting illustration of the preparation of the anode component anion represented by formula (I) according to the present invention is provided with reference to the following Scheme-(1), wherein ^R1 is a divalent n-propane linking group.

Add 200 mL dimethylformamide (DMF) and 10 g (1) fenthiamine (50.2 mmol) to a dried 3-neck, 500 ml round-bottomed flask equipped with a magnetic stirrer. The solution was stirred while purging with nitrogen for 1 hour. 2.4 g of 60% NaH (60 mmol) were added to the reaction mixture. The solution was observed to turn into a deep red color with the formation of bubbles in it. After one hour of continued mixing under nitrogen, the cessation of bubble generation was observed. Under a nitrogen purge, 6.6 g (2) 1,3-propane sultone (55.2 mmol) dissolved in 10 g anhydrous DMF was added dropwise to the contents of the flask. After completion of the addition of (2) 1,3-propane sultone, the reaction mixture was stirred at room temperature under nitrogen for 18 hours.

The reaction was quenched by adding 100 mL of deionized (DI) water and the solvent was removed by applying vacuum, leaving an oily material in the flask. 50 mL of ethyl acetate was added to the oily mass, which caused the formation of a precipitate, which was collected by vacuum filtration. The precipitate was washed with cold ethyl acetate and dried in vacuum at 60°C overnight to obtain the desired product (3) 3-(10 H -phenythiol-10-yl)-propane- as an off-white solid. 1-Sodium sulfonate. Process- (1) Synthesis example 2

Referring to the following Scheme-(2), a non-limiting illustration of the preparation of the anode component anion represented by formula (II) according to the present invention is provided, wherein R ² is a divalent n-propane linking group and R ³ is trifluoromethyl base.

Preparation of (3) sodium 3-(10 H -phenanthiol-10-yl)-propane-1-sulfonate was performed according to Synthesis Example 1. Finely grind one gram (0.0029 mol) of (3) sodium 3-( 10H -phenythiol-10-yl)propane-1-sulfonate in a mortar and pestle, and then purge/surround with _N2 Place in a 100 mL round bottom flask equipped with a magnetic stir bar and reflux condenser. An amount of 20 ml of acetone and 40 mg of 18-crown-6 ether were added to the flask and the mixture was stirred vigorously for 15 minutes. The solution became turbid, but the presence of solid sodium salt (3) was observed. Under _N2 , add (4) cyanogen chloride (540 mg, 0.0029 mol, 1 equiv) with vigorous stirring. The mixture was refluxed on an oil bath (at about 80°C) for 24 hours. The color of the solution changes to orange and a fine precipitate forms. Large chunks of the initial Na salt (3) are no longer observable. Thin layer chromatography (TLC) confirmed the presence of a single reaction product, which turned pink in air upon exposure to shortwave (316 nm) UV, demonstrating the formation of (5) 3-(10H-phenythiol-10-yl)- Propane-1-sulfonyl chloride. Product (5) has high mobility in 50:50 EtOAc/hexane. The reaction mixture was cooled to room temperature and filtered through a thin layer of alumina. The solvent was removed in vacuo to obtain 1.25 g of an orange-yellow glassy solid (5) . Product (5) was dissolved in MeCN and the solid was filtered off. The filtrate was used in the next step without additional purification.

(6) Trifluoromethanesulfonamide (4.53 g, 0.0305 mol, 1.05 equivalents) and potassium carbonate (40 g, 0.29 mol, 10 equivalents) were placed in a reflux condenser equipped with a magnetic stirring rod and Schrank 500 ml 3-neck flask with fritted Schlenk funnel. Connect the nitrogen feed end to the condenser and Schrank funnel and secure it with plastic clamps. Flush the container with a strong stream of nitrogen for 15 seconds and install a septum in the remaining neck. Add anhydrous MeCN in an amount of 100 ml through the septum using a syringe. The mixture was stirred vigorously for 20 minutes, resulting in a white cloudy dispersion. Add 50 ml of anhydrous MeCN to crude (5) 3-(10 H -phenanthiol-10-yl)propane-1-sulfonyl chloride (9.84 g, 0.029 mol) (filtrate from the previous step), and The resulting solution was transferred to a Schrank sintered funnel. The Schrank funnel was purged with nitrogen and plugged with a stopper held by a clamp. A solution of MeCN and (5) 3-( 10H -phenanthiol-10-yl)propane-1-sulfonyl chloride was added dropwise to a 3-neck flask over a period of one hour at room temperature. The contents of the 3-neck flask were refluxed for 24 hours. The formation of large precipitates was observed. The precipitate was filtered off and the resulting solution was concentrated in vacuo. The residue was recrystallized from water to obtain the product (7) 3-(10H-phenanthiol-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonate as brown needles. Potassium amide. Process- (2) Part -2

An electrochromic device according to the present invention was prepared according to the following procedure. Prepare the following initial solutions under magnetic stirring: propyl carbonate (7 g); ethyl carbonate (3 g); 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonimide ( EMIM-TFSI) (1 g); 3-(10 H -phenthiol-10-yl)-N-trifluoromethanesulfonylpropane-1-sulfonamide potassium (PTTK) (100 mg); and 1 ,1'-diethyl-4,4'-bipyridinium bis(trifluoromethane)sulfonimide (diethyl viologen TFSI) (100 mg). The addition of 3.5 g of polyacrylonitrile to the initial solution followed by homogenization resulted in the formation of a viscous slurry. A squeegee was used to form a liquid film of viscous slurry to a thickness of 400 microns (μm) on a sacrificial polyethylene terephthalate (PET) liner. The liquid film was heated to 70°C for 10 minutes, causing the formation of a solidified film/layer, which was the electrochromic layer. Separate the cured film/electrochromic layer from the sacrificial/temporary liner, cut to one size (2'' x 3''; 5.08 cm x 7.62 cm), and place on fluorine-doped tin oxide ( FTO)-glass electrode (3'' x 4''; 7.62 cm x 10.16 cm) that had a copper tape wrapped around the edges covered with insulating polyimide. A prefabricated thermoplastic spacer of 0.5'' (1.27 cm) width and 400 micron thickness was added surrounding the active area. A second fluorine-doped tin oxide (FTO)-glass is placed on the electrochromic layer. The stack was subjected to vacuum lamination at 140°C for 15 minutes to allow the gaskets to completely melt and seal. After cooling, the thus formed electrochromic device was removed from the vacuum lamination apparatus. Part -3

The percent transmission versus wavelength (nm) of the electrochromic device of Part-2 in the clear/unactivated state and the dark/activated state (in each case, at room temperature) is plotted in Figure 2 of the drawings . Referring to Figure 2, electrochromic devices according to the present invention provide a significant and desirable level of darkening (ie, reduced visible light transmission) upon activation compared to the clear/unactivated state. In Figure 2, the electrochromic device of Part-2 is described as "PTTK-ethyl viologen device". Further reference to Figure 2: The relationship between the transmission percentage and wavelength in the transparent/unactivated state is marked as "PTTK-EV, transparent"; and the relationship between the transmission percentage and wavelength in the darkened/activated state is marked as "PTTK-EV" , dark color".

The present invention has been described with reference to specific details of specific embodiments of the invention. Such details are not intended to be construed as limiting the scope of the invention except when included in the appended claims.

3: Electrochromic device 11: First substrate 14,26: first surface 17,29: Second surface 20: First transparent electrode layer 21: First electrical conductor 23:Second substrate 32: Second transparent electrode layer 33: Second electrical conductor 35: Electrochromic layer

Figure 1 is a representative side elevational cross-sectional view of an electrochromic device according to the present invention; and

Figure 2 is a graphical representation of percent transmission versus wavelength obtained from an electrochromic device according to the present invention in the activated (dark) and unactivated (clear) states, as described in the examples herein.

In Figures 1 and 2, similar features always refer to the same components and/or elements unless stated otherwise.

3: Electrochromic device

11: First substrate

14,26: first surface

17,29: Second surface

20: First transparent electrode layer

21: First electrical conductor

23:Second substrate

32: Second transparent electrode layer

33: Second electrical conductor

35: Electrochromic layer

Claims (32)

An electrochromic device comprising: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer surface, wherein the first transparent electrode layer and the second transparent electrode layer are relatively spaced apart from each other; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent conductive electrode layer between, wherein the electrochromic layer comprises: (i) a cathode component, (ii) an anode component comprising at least one anion selected from the anode component represented by the following formula (I) or formula (II) One anode component anion: (I) (II) wherein for formula (I), R ¹ is selected from a divalent straight or branched chain alkane linker, and wherein for formula (II), R ² is selected from a divalent straight or branched alkane linker. group, and R ³ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluoroalkyl, (iii) an optional electrolyte, and (iv) a polymer matrix. The electrochromic device of claim 1, wherein for formula (I), R ¹ is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group, and wherein for formula (II), R ² is is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, a linear or branched C ₁ -C ₁₀ fluorinated alkyl group, or a linear or branched C ₁ - C ₁₀ perfluoroalkyl. The electrochromic device of claim 2, wherein for formula (I), R ¹ is selected from divalent linear or branched chain C ₁ -C ₅ alkyl, and wherein for formula (II), R ² is selected from A divalent linear or branched chain C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched chain C ₁ -C ₅ perfluorinated alkyl group. The electrochromic device of claim 1, wherein the anode component further includes a counter cation. The electrochromic device of claim 4, wherein each relative cation is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations. The electrochromic device of claim 5, wherein each relative cation is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations. The electrochromic device of claim 1, wherein the cathode component includes at least one of the following: a 1,1'-disubstituted 4,4'-dipyridinium cation represented by the following formula (III), Or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted 4,4'-dipyridinium) cation represented by the following formula (VI): (III) (IV) Wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and R ⁷ is selected from divalent Straight chain or branched C ₁ -C ₁₀ alkane linking group. The electrochromic device of claim 7, wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl, and R ⁷ is selected from divalent linear or branched C ₁ -C ₈ alkane linking groups. The electrochromic device of claim 7, wherein the cathode component further includes a relative anion, wherein each relative anion of the cathode component is selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- and B(phenyl) ₄ ^- . The electrochromic device of claim 1, wherein the electrolyte is present and includes: at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(linear or branched chain C ₁ -C ₆ alkyl) sulfonyl)imine, and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(linear or branched chain C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ - C ₆ alkyl) imidazolium, 1-(linear or branched chain C ₁ -C ₆ alkyl)-1-(linear or branched chain C _{1 -C 6 alkyl) piperidinium, tetrakis (linear or branched chain C 1} -C ₆ alkyl) Branched chain C ₁ -C ₆ )ammonium or tris(C ₅ -C ₈ cycloalkyl)-(linear or branched chain C ₁ -C ₆ alkyl)ammonium. The electrochromic device of claim 1, wherein the polymer matrix includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride), (vinylidene fluoride-co-perfluoro (linear or branched C ₁ -C ₆ alkyl)) or poly((linear or branched C ₁ -C ₈ alkyl) (meth)acrylate) . An electrochromic composition comprising: (i) a cathode component, (ii) an anode component comprising at least one anion selected from the anode component represented by the following formula (I) or formula (II) An anode component anion: (I) (II) wherein for formula (I), R ¹ is selected from a divalent straight or branched chain alkane linker, and wherein for formula (II), R ² is selected from a divalent straight or branched alkane linker. group, and R ³ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluoroalkyl, (iii) an optional electrolyte, (iv) a polymeric thickener; and (iii) an optional electrolyte; v) A solvent. The electrochromic composition of claim 12, wherein for formula (I), R ¹ is selected from a divalent linear or branched chain C ₁ -C ₁₀ alkane linking group, and wherein for formula (II), R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, a linear or branched C ₁ -C ₁₀ fluorinated alkyl group, or a linear or branched C ₁ -C ₁₀ perfluoroalkyl. For the electrochromic composition of claim 13, for formula (I), R ¹ is selected from divalent linear or branched chain C ₁ -C ₅ alkyl groups, and wherein for formula (II), R ² is selected from A divalent linear or branched chain C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched chain C ₁ -C ₅ perfluorinated alkyl group. The electrochromic composition of claim 12, wherein the anode component further includes a counter cation. The electrochromic composition of claim 15, wherein each relative cation is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations. The electrochromic composition of claim 16, wherein each relative cation is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations. The electrochromic composition of claim 12, wherein the cathode component includes at least one of the following: a 1,1'-disubstituted 4,4'-dipyridinium cation represented by the following formula (III) , or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted 4,4'-dipyridinium) cation represented by the following formula (VI): Formula (III) Formula (IV) Wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl, unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ - C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₁₀ alkyl , unsubstituted C ₃ -C ₇ cycloalkyl, substituted C ₃ -C ₇ cycloalkyl, unsubstituted aryl and substituted aryl, and R ⁷ is selected from divalent straight chain or Branched chain C ₁ -C ₁₀ alkane linking group. The electrochromic composition of claim 18, wherein for formula (III), R ⁴ and R ⁵ are each independently selected from linear or branched C ₁ -C ₄ alkyl, unsubstituted phenyl and Substituted phenyl, and wherein for formula (IV), R ⁶ and R ⁸ are each independently selected from linear or branched chain C ₁ -C ₄ alkyl, unsubstituted phenyl and substituted phenyl, And R ⁷ is selected from divalent straight chain or branched chain C ₁ -C ₈ alkane linking groups. The electrochromic composition of claim 18, wherein the cathode component further includes a relative anion, wherein each relative anion of the cathode component is selected from the group consisting of: BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- and B(phenyl) ₄ ^- . The electrochromic composition of claim 12, wherein the electrolyte is present and includes: at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro (linear or branched chain C ₁ -C ₆ alkane) sulfonyl)imine, and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(linear or branched chain C ₁ -C ₆ alkyl)-3-(linear or branched chain C ₁ -C ₆ alkyl) imidazolium, 1-(linear or branched chain C ₁ -C ₆ alkyl) -1-(linear or branched chain C ₁ -C ₆ alkyl) piperidinium, tetrakis (linear Or branched chain C ₁ -C ₆ ) ammonium or tris (C ₅ -C ₈ cycloalkyl)-(linear or branched chain C ₁ -C ₆ alkyl) ammonium. The electrochromic composition of claim 12, wherein the polymeric thickener includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride) , poly(vinylidene fluoride-co-perfluoro(linear or branched chain C ₁ -C ₆ alkyl)) or poly((linear or branched chain C ₁ -C ₈ alkyl) (meth)acrylic acid ester). The electrochromic composition of claim 12, wherein the solvent contains at least one of the following: ethyl carbonate, propyl carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone , polyethylene glycol, polyethylene glycol carboxylic acid ester, cyclotenine, α,ω-(C ₂ -C ₈ ) dinitrile or bis (linear or branched chain C ₁ -C ₈ ) acetamide. A compound represented by the following formula (IIa): (IIa) wherein R ² is selected from divalent linear or branched chain alkane linking groups; and R ³ is selected from fluorine, linear or branched chain fluorinated alkyl, or linear or branched chain perfluorinated alkyl. The compound of claim 24, wherein R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group; and R ³ is selected from fluorine, linear or branched C ₁ -C ₁₀ fluorinated Alkyl or linear or branched chain C ₁ -C ₁₀ perfluorinated alkyl. The compound of claim 25, wherein R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched C ₁ -C ₅ perfluorinated alkane. base. A salt containing an anion represented by the following formula (II): (II) wherein R ¹ is selected from a divalent linear or branched chain alkane linking group; and R ² is selected from fluorine, a linear or branched chain fluorinated alkyl group, or a linear or branched chain perfluorinated alkyl group. The salt of claim 27, wherein for the anion represented by formula (II), R ² is selected from a divalent linear or branched C ₁ -C ₁₀ alkane linking group, and R ³ is selected from fluorine, linear Chain or branched chain C ₁ -C ₁₀ fluorinated alkyl group or straight chain or branched chain C ₁ -C ₁₀ perfluorinated alkyl group. The salt of claim 28, wherein for the anion represented by formula (II), R ² is selected from a divalent linear or branched C ₁ -C ₅ alkane linking group; and R ³ is selected from a linear or branched chain C 1 -C 5 alkane linking group; Branched chain C ₁ -C ₅ perfluoroalkyl. The salt of claim 27, wherein the salt further contains a counter cation. The salt of claim 30, wherein each relative cation is independently selected from tetrakis (linear or branched chain alkyl) ammonium cations. The salt of claim 31, wherein each relative cation is independently selected from tetrakis (linear or branched chain C ₁ -C ₁₀ alkyl) ammonium cations.