Electrochromic devices and compositions containing poly((diallyldimethylammonium bis(substituted sulfonyl)imide anion))

Abstract

The present invention relates to poly(diallyldimethylammonium bis(substituted sulfonyl)imide X - )) Electrochromic devices and compositions containing a polymer matrix or thickener containing a polymer, - are independently represented by the following formula (A): [Formula 1] JPEG2025514936000041.jpg2858 (Referring to formula (A), R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. is an anion represented by

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the right to and priority to U.S. Provisional Patent Application No. 63 / 333,219, filed April 21, 2022, and U.S. Nonprovisional Patent Application No. 18 / 133,000, filed April 11, 2023, the disclosures of each of which are incorporated by reference in their entirety herein.

[0002] The present invention relates to electrochromic devices and compositions that include a polymer matrix or thickener that includes poly((diallyldimethylammonium bis(substituted sulfonyl)imide anion)) as the polymer. [Background technology]

[0003] Electrochromism involves a reversible change in the visible color and / or transmittance of a material upon application of an electric potential. The change in color and / or transmittance typically involves cycling through alternating oxidation and reduction charge states. In general, materials that develop color upon reduction are referred to as cathodically coloring electrochromic materials, and materials that develop color upon oxidation are referred to as anodically coloring electrochromic materials.

[0004] Electrochromic devices typically include an electrochromic layer interposed between separate and opposing transparent electrode layers of separate and opposing substrates. The electrochromic layer typically includes a polymer matrix whose cathodic and anodic components are transported toward the respective cathodes and anodes where corresponding reduction and oxidation reactions occur, at least one of which results in a change in color and / or transmittance of visible light through the electrochromic device.

[0005] The kinetics of electrochromic devices are typically dominated by mass transport of cathodic and anodic components across or through the electrochromic layer. Due to charge exchange, the currents of both electrodes (cathode and anode) are necessarily equal. If one of the components (cathode or anode component) moves or transports more slowly through or across the electrochromic layer, typically a higher concentration of that component is required, more specifically, a higher concentration gradient (higher interfacial concentration) of the slower moving / transported component at the electrode interface is required to equalize the diffusion flux and maintain a given current. Adjusting and / or maintaining a higher concentration of the component with reduced mass transport may require additional preparation and / or manufacturing steps and may result in inadvertent formulation errors. Mass transport imbalance may, in some cases, result in reduced durability of the electrochromic device, especially if the slower mass transporting active component undergoes over-oxidation or over-reduction at a particular electrode.

[0006] The polymer matrix of the electrochromic layer typically comprises a polymer. The polymer of the polymer matrix can significantly affect the transport properties of the cathode and anode components therethrough. In addition, the polymer of the polymer matrix can affect the adhesion properties of the electrochromic layer. Poor adhesion properties can result in undesirable separation and / or delamination of the transparent electrode layer and associated substrate from the electrochromic layer. The polymer of the electrochromic layer can also affect the transparency of the electrochromic device. In some cases, low solubility of the components in the polymer of the electrochromic layer can result in an undesirable increase in haze, which correspondingly adversely affects the transparency of the electrochromic device. The polymer can affect the durability and high temperature performance of the electrochromic layer. For example, the degradation of the polymer over time can result in an undesirable decrease in the durability and high temperature performance of the electrochromic layer and the corresponding electrochromic device.

[0007] It would be desirable to develop new polymers for use in forming the polymer matrix of the electrochromic layers of electrochromic devices. It would be further desirable for such newly developed polymers to provide properties that are at least as good as, and preferably better than, those of existing polymers, such as, but not limited to, balanced mass transport properties, reduced haze, reduced or low current density, improved high temperature performance, and / or improved adhesion properties. Summary of the Invention

[0008] According to the present invention, there is provided an electrochromic device comprising: (a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface with a second transparent conductive electrode layer, the first transparent electrode layer and the second transparent electrode layer being opposed to each other with a space therebetween; and (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer. The electrochromic layer comprises: (i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; and (iv) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X). - ), each X - are independently represented by the following formula (A): [ka] (In the formula, R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. and a polymer matrix,

[0009] According to the present invention, there is further provided an electrochromic device comprising: (a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface with a second transparent conductive electrode layer, the first transparent electrode layer and the second transparent electrode layer being spaced apart from each other and facing each other; and (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer. The electrochromic layer comprises: (i) an electrochromic material comprising a cathodic component having a cationic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having a covalently bonded anion; (ii) an optional electrolyte; and (iii) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - is independently an anion represented by formula (A) above, and a polymer matrix.

[0010] The present invention further provides a polymeric thickener comprising: (i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; and (iv) a polymer, the polymer being poly(diallyldimethylammonium xylene). - ), each X - is independently an anion represented by formula (A) above; and (v) a solvent.

[0011] In accordance with the present invention, there is provided a method for preparing a thickener comprising: (i) a cathode component having a cationic charge, said cathode component further comprising a counter anion, each counter anion of said cathode component being an anode component having a covalently bound anion; (ii) an optional electrolyte; and (iii) a polymeric thickener comprising a polymer, said polymer being poly(diallyldimethylammonium xanthate). - ), each X - Further provided is an electrochromic composition comprising: a polymeric thickener, wherein each of the polymeric thickeners is independently an anion represented by formula (A) above; and (iv) a solvent.

[0012] The features which characterize the present invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. These and other features of the present invention, its operating advantages, and particular objects attained by its uses will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are shown and described. [Brief description of the drawings]

[0013] [Figure 1] 1 is a representative cross-sectional side view of an electrochromic device according to the present invention.

[0014] [Diagram 2] Photograph of an electrochromic device according to the present invention, as described in the Examples, in the transparent / inactive state (a) on the left and in the dark / active state (b) on the right.

[0015] In Figures 1 and 2, like characters may refer to the same components and / or elements, unless otherwise stated. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] As used herein, the articles "a," "an," and "the" include plural referents unless specifically and unambiguously limited to one referent.

[0017] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to encompass any and all values ​​and subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all values ​​therebetween (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), and subranges between (and including) a minimum value of 1 and a maximum value of 10, i.e., all subranges or subratios beginning with a minimum value of 1 or greater and ending 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.

[0018] As used herein, unless otherwise indicated, a left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as, but not limited to, a right-to-left orientation. [ka] or equivalently, the left-to-right representation of -C(O)O- is [ka] or equivalently, -O(O)C- or -OC(O)-.

[0019] Other than in the working examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about."

[0020] 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.

[0021] 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).

[0022] As used herein, the term "polymer" refers to homopolymers (eg, prepared from a single monomer type), copolymers (eg, prepared from at least two monomer types), and graft polymers.

[0023] As used herein, the term "(meth)acrylate" and similar terms such as "(meth)acrylic acid ester" refer to methacrylate and / or acrylate. As used herein, the term "(meth)acrylic acid" refers to methacrylic acid and / or acrylic acid.

[0024] As used herein, the term "electrochromic" and similar terms such as "electrochromic compound" refer to having an absorption spectrum of at least visible radiation that changes in response to the application of an electric potential. Additionally, as used herein, the term "electrochromic material" refers to any substance that is adapted to exhibit electrochromic properties (e.g., adapted to have an absorption spectrum of at least visible radiation that changes in response to an applied electric potential) and that includes at least one electrochromic compound.

[0025] As used herein, the term "electric potential" and related terms such as "electrical potential" refer to an electrical potential that can cause a response in a material, such as, but not limited to, transforming an electrochromic material from one form or state to another, as described in more detail herein.

[0026] The terms "first" and "second", when used herein to modify the term "state", are not intended to refer to a particular order or chronological sequence, but instead refer to two different conditions or properties. For non-limiting illustration, the first and second states of an electrochromic compound, e.g., anodically coloring electrochromic compound, may differ with respect to at least one optical property, e.g., but not limited to, the absorption of visible light and / or UV light. Thus, according to various non-limiting embodiments disclosed herein, the anodically coloring electrochromic compound of the present invention may have different absorption spectra in each of the first and second states. For example, but not limited herein, the anodically coloring electrochromic compound may be transparent in the first state and colored in the second state. Alternatively, the anodically coloring electrochromic compound may have a first color in the first state and a second color in the second state.

[0027] As used herein, the term "indication" means a visible or machine-readable representation of information in words, numbers, symbols, designs, or drawings. Non-limiting examples of indicia include screens, monitors, and security elements such as security markings.

[0028] As used herein, the term "window" means an opening adapted to allow the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and light switches.

[0029] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0030] As used herein, spatial or directional terms such as "left," "right," "inner," "outer," "upper," "lower," and the like, refer to the present invention as depicted in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and thus such terms should not be considered limiting.

[0031] As used herein, the terms "formed on," "deposited on," "provided on," "applied on," "existing on," or "disposed on" mean formed, deposited, provided, applied, present, or disposed on, but not necessarily in direct (or abutting) contact with an underlying element or a surface of an underlying element. For example, a layer "disposed on" a substrate does not exclude the presence of one or more other layers, coatings, or films of the same or different composition located between the disposed or formed layer and the substrate.

[0032] As used herein, the terms "intervening" and "intervening between" mean present or disposed between, but not necessarily in direct (or abutting) contact with, overlying and / or underlying elements or surfaces thereof. For example, an "intervening" layer between a first substrate and a second substrate does not exclude the presence of one or more other layers, coatings, or films of the same or different composition located between the intervening layer and the first and / or second substrate.

[0033] All documents, including but not limited to issued patents and patent applications, are referenced herein and should be considered "incorporated by reference" in their entirety unless otherwise indicated.

[0034] As used herein, the recitation of a "straight or branched" group, such as a straight or branched alkyl, is understood herein to include: a methylene or methyl group; a straight chain group, such as a straight chain C 2 ~C 20 Alkyl groups; and suitably branched groups, such as branched C 3 ~C 20 Alkyl group.

[0035] As used herein, the term "alkyl" refers to straight or branched chain, cyclic or non-cyclic C 1 ~C 25A straight or branched chain alkyl is a C 1 ~C 25 Alkyl, e.g. C 1 ~C 20 Alkyl, e.g. C 2 ~C 10 Alkyl, e.g. C 1 ~C 12 Alkyl, e.g. C 1 ~C 6 Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, those further listed herein. The alkyl group may include a "cycloalkyl" group. As used herein, the term "cycloalkyl" refers to a group that is suitably cyclic, 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 It means a cycloalkyl group (including alkyl). Examples of cycloalkyl groups include, but are not limited to, those further enumerated herein. The term "cycloalkyl" as used herein also includes bridged-ring polycycloalkyl groups (or bridged-ring polycyclic alkyl groups), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and fused-ring polycycloalkyl groups (or fused-ring polycyclic alkyl groups), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthalenyl.

[0036] As used herein, the term "heterocycloalkyl" refers to a suitably cyclic group having at least one heteroatom in the 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 groups, such as C 2 ~C 10 Heterocycloalkyl groups, such as C 5 ~C 7means a heterocycloalkyl group. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl and piperidinyl. The term "heterocycloalkyl" as used herein also includes bridged ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0037] The descriptions, classes, and examples provided herein with respect to alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, and the like, are also applicable to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, and the like, including, but not limited to, polyvalent alkane groups, e.g., polyvalent alkane linking groups, e.g., divalent alkane linking groups.

[0038] As used herein, the term "aryl" and related terms such as "aryl group" refer to an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term "aromatic" and related terms such as "aromatic group" refer to a cyclic conjugated hydrocarbon having a stability (due to delocalization of π electrons) significantly greater than the stability of a hypothetical localized structure. Examples of aryl groups include C 6 ~C 14 Aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl.

[0039] The term "heteroaryl" as used herein includes, but is not limited to, C 3 ~C 18 Heteroaryl, such as, but not limited to, C 3 ~C 10Heteroaryl (including fused-ring polycyclic heteroaryl groups) refers to an aryl group having at least one heteroatom in an aromatic ring or, in the case of a fused-ring polycyclic heteroaryl group, in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, and pyrimidinyl.

[0040] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 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.

[0041] As used herein, the term "nitrogen-containing heterocycle", e.g., "nitrogen-containing heterocyclic group" or "nitrogen-containing heterocyclic substituent", includes, but is not limited to, a nitrogen-containing ring in which the nitrogen-containing ring is bonded via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amino (or alicyclic amino), e.g., morpholino, piperidino, pyrrolidino, and decahydroisoquinolino; and heteroaromatic compounds, e.g., imidazole, pyrrole, indole, carbazole.

[0042] As used herein, the recitation of "substituted" groups refers to groups including, but not limited to, alkyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, and / or heteroaryl groups, in which at least one hydrogen has been replaced with a group or "substituent" other than hydrogen, such as, but not limited to, alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; carboxylate groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate ester groups; nitro groups; cyano groups; alkyl groups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups (including alkaryl groups, including hydroxyl substituted aryls such as phenols, including poly-fused ring aryls); aralkyl groups; heteroaryl groups (including poly-fused ring heteroaryl groups); amino groups, such as -N(R 11’ )(R 12’ )(wherein, R 11’ and R 12’ are each independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, or heteroaryl; a carboxylate group; a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a carbamate group; a carbonate group; a urea group; a trialkylsilyl group; a nitrogen-containing heterocycle; or combinations thereof, including classes and examples as further described herein. According to some embodiments of the present invention, the substitutents of the substituted group are more specifically recited.

[0043] As used herein, the term "halo" and related terms such as "halo group," "halo substituent," "halogen group," and "halogen substituent" refer to a single-bonded halogen radical, e.g., -F, -Cl, -Br, and -I.

[0044] As used herein, the recitation of "halo-substituted" and related terms (e.g., but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and haloheteroaryl) refers to a group having at least one to all (including all) of its available hydrogen radicals replaced with a halo radical, e.g., but not limited to, F, Cl, or Br. The term "halo-substituted" includes "perhalo-substituted." As used herein, the term perhalo-substituent and related terms (e.g., but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl, or perhaloheteroaryl) refers to a group having all of its available hydrogen radicals replaced with a halo radical. For non-limiting illustration, perhalomethyl is -CX 3 and perhalophenyl is -C 6 X 5 where X represents one or more halo groups, such as, but not limited to, F, Cl, Br or I.

[0045] As used herein, "at least one" is synonymous with "one or more," regardless of whether the elements are listed conjunctively or disjunctively. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" mean any one of A, B, or C, or any combination of any two or more of A, B, or C, respectively. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0046] As used herein, "selected from" is synonymous with "chosen from," regardless of whether the elements are listed conjunctively or disjunctively. Furthermore, the phrases "selected from A, B, and C" and "selected from A, B, or C" mean any one of A, B, or C, respectively, or any combination of any two or more of A, B, or 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 of A, B, and C.

[0047] The description of the invention herein may describe certain features as being "particularly" or "preferably" within certain limits (e.g., "preferably," "more preferably," or "even more preferably" within certain limits). It is to be understood that the invention is not limited to such specific or preferred limits, but rather encompasses the full scope of the disclosure.

[0048] As used herein, and according to some embodiments, the term "ketone" and related terms such as "ketone group" and "ketone substituent," in reference to groups and substituents of various groups of the compounds and components of the invention, include materials represented by -C(O)R, where R is selected from the groups described below except hydrogen.

[0049] As used herein, and according to some embodiments, the term "carboxylic acid" and related terms such as "carboxylic acid group" and "carboxylic acid substituent," in reference to groups and substituents of various groups of the compounds and components of the invention, includes materials represented by -C(O)OH.

[0050] As used herein, and according to some embodiments, the term "ester" with respect to groups and substituents of various groups of the compounds and components of the invention, and related terms such as "ester group" and "ester substituent", refers to a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups described below except hydrogen.

[0051] As used herein, and according to some embodiments, the term "carboxylate" and related terms such as "carboxylate group" and "carboxylate substituent," in reference to groups and substituents of various groups of the compounds and components of the invention, includes materials represented by -OC(O)R, where R is selected from the groups described below.

[0052] As used herein, and according to some embodiments, the term "amide" and related terms such as "amide group" and "amide substituent," in reference to groups and substituents of various groups of the compounds and components of the invention, includes materials represented by -C(O)N(R)(R) or -N(R)C(O)R, where each R is independently selected from the groups described below.

[0053] As used herein, and according to some embodiments, the term "carbonate" and related terms such as "carbonate group" and "carbonate substituent," in reference to groups and substituents of various groups of the compounds and components of the invention, include materials represented by -OC(O)OR, where R is selected from the groups described below except hydrogen.

[0054] As used herein, and according to some embodiments, the term "carbamate" and related terms such as "carbamate group" and "carbamate substituent", in reference to groups and substituents of various groups of compounds and components of the invention, includes materials represented by -OC(O)N(R)(H) or -N(H)C(O)OR, where R is independently selected at each occurrence from the groups described below other than hydrogen.

[0055] As used herein, and according to some embodiments, the term "urea" and related terms such as "urea group" and "urea substituent", in reference to groups and substituents of various groups of the compounds and components of the invention, includes materials represented by -N(R)C(O)N(R)(R), where each R is independently selected from the groups described below.

[0056] As used herein, and according to some embodiments, the term "siloxy" with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms such as "siloxy group" and "siloxy substituent" refer to -O-Si(R) 3 wherein each R is independently selected from the groups described below other than hydrogen.

[0057] As used herein, and according to some embodiments, the term "alkoxysilane" and related terms such as "alkoxysilane group" and alkoxysilane substituents, with respect to groups and various group substituents of the compounds and components of the present invention, refers to -Si(OR'') w (R) t wherein w is 1 to 3, t is 0 to 2, with the proviso that the sum of w and t is 3, R″ for each w is independently selected from alkyl, and R for each t is independently selected from the following groups other than hydrogen:

[0058] As used herein, and according to some embodiments, the term "polysiloxane" and related terms such as "polysiloxane group" and "polysiloxane substituent" in relation to groups and substituents of various groups of the compounds and components of the present invention refer to a compound having the following formula (C): [ka] The present invention includes materials represented by

[0059] With reference to formula (C), t' is 2 or more, for example, 2 to 200; R for each t' is f and Rg are each independently selected from the group R described below other than hydrogen; R h are independently a group R described below.

[0060] Unless otherwise specified, each R group in each of the above ketone, ester (carboxylic acid ester), carboxylate, amide, carbonate, carbamate, urea, siloxane, alkoxysilane groups, and polysiloxane groups is independently selected at each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including the classes and examples thereof listed herein above.

[0061] According to the present invention, the electrochromic material (of the electrochromic layer of the electrochromic element) comprises a polymer matrix, the polymer matrix being poly(diallyldimethylammonium x - ), each X - are independently represented by the following formula (A): [ka] is an anion represented by

[0062] With reference to formula (A), the term "linear or branched fluorinated alkyl" means an alkyl group in which at least one, and if not all, available hydrogens are replaced with a fluoro group (F).

[0063] In some embodiments, R of formula (A) 9 and R 10 each independently represents fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0064] In some further embodiments, R of formula (A) 9 and R 10 each independently represents a linear or branched chain C 1 ~C 5 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0065] In some further embodiments, R of formula (A) 9 and R 10 are each trifluoromethyl, and the polymer of the polymer matrix comprises poly((diallyldimethylammonium) bis(trifluoromethane)sulfonimide)), also referred to herein as poly((diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide).

[0066] Poly(diallyldimethylammonium x) in the polymer matrix of the electrochromic layer - The bis(diallyldimethylammonium bis(substituted sulfonyl)imide anion) polymer may also be referred to herein as poly((diallyldimethylammonium bis(substituted sulfonyl)imide anion)), where the substituents of each substituted sulfonyl moiety thereof are independently selected from the R groups described with reference to formula (A). 9 and R 10 is selected from.

[0067] In some embodiments, the poly(diallyldimethylammonium X-) polymer of the polymer matrix has the following formula (B): [ka] The above can be described with reference to the above.

[0068] With respect to formula (B), each X -are independently anions represented by formula (A) hereinbefore. In view of the difficulty in determining the Mn of poly(diallyldimethylammonium) polymers such as those represented by formula (B), and without intending to be bound by any theory, n in formula (B) is estimated to be at least 2, e.g., from 2 to at least 1000, or from 50 to at least 1000, in some embodiments.

[0069] Poly(diallyldimethylammonium x) - ) The polymer, in some embodiments of the invention, has a Mw of less than 100 kDa, or between 200 and 350 kDa, or between 400 and 500 kDa.

[0070] Poly(diallyldimethylammonium x) - ) Polymers, in some embodiments, can be prepared according to the non-limiting synthetic descriptions provided in the examples further herein.

[0071] The polymer matrix, in some embodiments, is present in the electrochromic layer in an amount of 5% to 80% by weight, or 10% to 60% by weight, or 15% to 50% by weight, in each case the weight percentage being based on the total weight of the electrochromic layer.

[0072] According to some embodiments of the present invention, the anode component has the following formula (I) or formula (II): [ka] The anodic component anion comprises at least one anodic component anion selected from the group consisting of

[0073] With reference to formulas (I) and (II), R 1 and R 2 are each independently selected from divalent straight or branched chain alkane linking groups. 3is selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

[0074] The anodic component anion can be described as comprising an anodic moiety (group or moiety), such as a (10H-phenothiazin-10-yl) moiety, and an anion covalently bonded to the anodic moiety, such as a sulfonate anion or a triflamide anion. In some further embodiments, the anion of the anodic component anion is covalently bonded to the anodic group or moiety by a divalent straight or branched chain alkane linking group. In some further embodiments, the anodic component anion is an anodically colored electrochromic compound or group to which the anion is covalently bonded.

[0075] According to some embodiments, and with reference to formulas (I) and (II), R 1 and R 2 each independently represents a divalent linear or branched C 1 ~C 10 In some embodiments, R is selected from the group consisting of alkane linking groups. 3 is fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0076] With further reference to formulas (I) and (II), and according to some embodiments, R 1 and R 2 each independently represents a divalent linear or branched C 1 ~C 5 With reference to formula (II), R 3 In some embodiments, linear or branched C 1 ~C 5 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0077] In some embodiments, R in formula (I) and (II) 1 and R 2are each independently selected from divalent methane, divalent ethane, divalent straight-chain or branched-chain propane, divalent straight-chain or branched-chain butane, and divalent straight-chain or branched-chain pentane. 3 is selected from fluorinated or perfluorinated versions or derivatives of methyl, ethyl, straight or branched chain propyl, straight or branched chain butyl, and straight or branched chain pentyl.

[0078] In some embodiments of the present invention, anodic component anions (having an anion covalently bound thereto), as represented by Formula (I) and Formula (II), can be prepared according to the non-limiting synthetic descriptions provided in the further examples herein.

[0079] References herein to a counterion (such as a countercation and / or counteranion) of a component refer, in some embodiments, to the counterion of the component when prepared separately from and / or prior to combination with the electrochromic layer and / or electrochromic composition of the present invention.

[0080] According to some further embodiments, the anode component comprising the anode component anion further comprises a counter cation. Examples of classes of cations from which each counter cation may be independently selected include alkali metal cations, such as lithium cations (Li + ), sodium cation (Na + ), and potassium cation (K + ); alkaline earth metal cations, e.g., 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 cations, and optionally substituted N,N-disubstituted morpholinium cations; 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 isoquinolinium cations; and tetrasubstituted ammonium cations, which are described in more detail below. The optional substituents of the classes and examples of ammonium cations can be selected from the classes and examples of substituents listed herein above, such as, but not limited to, linear or branched alkyl groups, cycloalkyl groups, and aryl groups. The N-substituted and N,N-disubstituted groups of the ammonium cations can be selected from the classes and examples of substituents listed herein above, such as, but not limited to, linear or branched alkyl groups, cycloalkyl groups, and aryl groups.

[0081] In some embodiments, the counter cation of the anodic component is a monocation. According to some further embodiments, the counter cation of the anodic component is a monocation represented by the following formula (D): [ka] The tetrasubstituted ammonium cation is selected from the group consisting of tetrasubstituted ammonium cations represented by

[0082] Referring to formula (D), R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl. With further reference to formula (D), R a , R b , R c and R d each independently represents a linear or branched chain C 1 ~C 10Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 The substituents of the substituted cycloalkyl and substituted phenyl groups can be independently selected from those listed herein above, such as, but not limited to, straight-chain or branched-chain alkyl groups, cycloalkyl groups, and aryl groups.

[0083] In some embodiments, with reference to formula (D), R a , R b , R c and R d Each of R is independently selected from linear or branched alkyl. a , R b , R c and R d each independently being a straight or branched chain C 1 ~C 10 is selected from alkyl.

[0084] In some embodiments, each counter cation of the anode components is independently selected from tetra(linear or branched chain alkyl)ammonium cations. In some further embodiments, each counter cation of the anode components is independently selected from tetra(linear or branched chain alkyl)ammonium cations. 1 ~C 10 alkyl) ammonium cations.

[0085] The anode component, in some embodiments, is composed of or otherwise consists of anode component anions selected from at least one anode component anion represented by Formula (I) or Formula (II) and counter cations, where the anode component has an equal number of anions and counter cations and a corresponding neutral charge.

[0086] According to some embodiments, in addition to or in place of the anode component anions to which, for example, anions represented by Formula (I) and / or Formula (II) are covalently bonded, the anode component of the electrochromic layer may comprise one or more additional anodic electrochromic compounds, such as, but not limited to, ferrocene or ferrocene derivatives (wherein at least one cyclopentadienyl ring is substituted with at least one substituent, including those listed herein above); 5,10-dihydro-5,10-di(straight or branched chain C 1 ~C 10 alkyl)phenazines, such as 5,10 dihydro-5,10 dimethylphenazine; N-substituted phenoxazines, such as N-phenylphenoxazine; and combinations thereof. According to some embodiments, when an additional anodic component is present (in addition to the anodic component anion to which the anion is covalently bound), an additional cathodic component (or additional suitable amounts of cathodic components) may also be present. In some embodiments, the additional cathodic component comprises one or more cathodic components represented by formula (III) and / or (IV).

[0087] Anode components, including but not limited to, anode components having covalently bound anions, in some embodiments, are present in the electrochromic layer in an amount of 0.25 wt % to 6.25 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 3 wt %, where the weight percentage in each case is based on the total weight of the electrochromic layer.

[0088] The cathode component of the electrochromic layer of the electrochromic device, in some embodiments, is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III): [ka] Includes at least one of the following:

[0089] With reference to formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 It is selected from cycloalkyl, unsubstituted aryl, and substituted aryl.

[0090] With reference to formula (IV), in some embodiments, R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C 1 ~C 10 The linking groups are selected from alkane linking groups.

[0091] R in formula (III) 4 and R 5 And R of formula (IV) 6 and R 8 The aryl groups of the unsubstituted and substituted aryl groups from which each may be independently selected include those aryl groups listed herein above, such as, but not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl. 4 and R 5 And R of formula (IV) 6 and R 8 The cycloalkyl groups of the unsubstituted and substituted cycloalkyl groups from which each may be independently selected include those cycloalkyl groups listed herein above, such as, but not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0092] R in formula (III) 4 and R 5And R of formula (IV) 6 and R 8 Substituents for the substituted cycloalkyl and aryl groups, each of which may be independently selected, include those listed herein above. In some embodiments, R 4 and R 5 And R of formula (IV) 6 and R 8 Each of the substituents of the substituted cycloalkyl and substituted aryl groups, which may each be independently selected, is each independently selected from alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups; aralkyl groups (e.g., benzyl groups); heteroaryl groups; and amino groups.

[0093] R in formula (III) 4 and R 5 And R of formula (IV) 6 and R 8 Straight-chain or branched-chain alkyl groups from which each may be independently selected include the classes and examples of alkyl groups listed hereinabove, such as, but not limited to, methyl, ethyl, straight-chain or branched-chain propyl, straight-chain or branched-chain butyl, straight-chain or branched-chain pentyl, straight-chain or branched-chain hexyl, and straight-chain or branched-chain heptyl.

[0094] With further reference to formula (III), according to some embodiments of the present invention, R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 4 It is selected from alkyl, unsubstituted phenyl, and substituted phenyl.

[0095] With further reference to formula (IV), according to some embodiments of the present invention, R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 4 R is selected from alkyl, unsubstituted phenyl, and substituted phenyl;7 is a divalent linear or branched C 1 ~C 8 In some further embodiments, R of formula (IV) is selected from the group consisting of alkane linking groups. 7 is a divalent linear or branched C 1 ~C 5 Alkane linking groups, e.g., divalent linear or branched C 3 ~C 5 It is an alkane linking group.

[0096] According to some embodiments of the present invention, the cathode component further comprises a counteranion. In some further embodiments, the cathode component comprises an equal number of cations and counteranions (or anions), such that the cathode component correspondingly has a net neutral charge. Each counteranion of the cathode component, in some embodiments, is independently BF 4 - , P.F. 6 - , ClO 4 - , C.F. 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , and B(phenyl) 4 - In some embodiments, the counter anion of the cathodic component does not include or is not selected from the anions of the anodic component as represented by formulas (I) and (II).

[0097] According to some embodiments of the present invention, the cathodic component having a cationic charge is present in the electrochromic layer in an amount of 0.25 wt % to 6.25 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 3 wt %, where the wt % in each case is based on the total weight of the electrochromic layer.

[0098] In some embodiments of the present invention, the electrochromic layer of the electrochromic device of the present invention comprises an electrolyte. The electrolyte, in some embodiments, comprises at least one electrolyte anion and at least one electrolyte cation. The electrolyte of the electrochromic layer, in some embodiments, comprises an equal number of electrolyte anions and electrolyte cations, and correspondingly has a net neutral charge.

[0099] In some embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, where each electrolyte anion is independently selected from the group consisting of chloride, hexafluorophosphate, and bis(perfluoro(linear or branched C 1 ~C 6 In some further embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte cation, each electrolyte cation being independently selected from sodium; potassium; lithium; ammonium cations, such as tetra(straight or branched chain C 1 ~C 6 Alkyl)ammonium and tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 1-(C alkyl) ammonium; 1 ~C 6 Alkyl)-3-(straight or branched chain C 1 ~C 6 Alkyl)imidazolium;1-(straight or branched chain C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 1-(Straight or branched chain C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 alkyl) piperidinium; or phosphonium cations, such as, but not limited to, tetra(straight or branched chain C 1 ~C 6 alkyl)phosphonium or tri(C5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 alkyl)phosphonium.

[0100] The electrolyte of the electrochromic layer, in some embodiments, is at least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched chain C 1 ~C 6 at least one electrolyte anion selected from the group consisting of 1-(straight or branched chain C alkylsulfonyl)imides; and at least one electrolyte cation, each electrolyte cation being independently selected from the group consisting of 1-(straight or branched chain C alkylsulfonyl)imides; 1 ~C 6 Alkyl)-3-(straight or branched C 1 ~C 6 Alkyl)imidazolium, 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 alkyl)pyrrolidinium, or 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 and at least one electrolyte cation selected from the group consisting of alkyl) piperidinium.

[0101] The electrolyte of the electrochromic layer, in some further embodiments, comprises at least one electrolyte anion, where each electrolyte anion is a bis(trifluoromethylsulfonyl)imide; and at least one electrolyte cation, where each electrolyte cation is independently selected from 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-1-butylpyrrolidinium, and 1-methyl-1-propylpiperidinium.

[0102] The electrolyte, in some embodiments, is present in the electrochromic layer in an amount of from 1 wt % to 75 wt %, or from 5 wt % to 50 wt %, or from 10 wt % to 30 wt %, where the weight percentage in each case is based on the total weight of the electrochromic layer.

[0103] According to some further embodiments, the electrochromic layer of the present invention includes a solvent. In some further embodiments, a solvent is present in the electrochromic layer instead of or in addition to the electrolyte. The solvent, in some embodiments, is ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C 2 ~C 8 ) dinitrile, or di(linear or branched C 1 ~C 8 ) acetamide. Without intending to be bound by any theory, it is believed that, according to some embodiments, the solvent acts, at least in part, as a plasticizer within (or plasticizes) the electrochromic layer. The solvent, in some embodiments, is present in the electrochromic layer in an amount of 10-75 wt %, or 20-60 wt %, with the weight percent in each case being based on the total weight of the electrochromic layer and the solvent.

[0104] In some embodiments of the present invention, poly(diallyldimethylammonium x) as previously described herein may be used. - In addition to the above, the polymer matrix may include a further polymer, such as 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).

[0105] The electrochromic layer of the electrochromic device of the present invention may further include one or more art-recognized additives in some embodiments, such as, but not limited to, thermal stabilizers, UV stabilizers, rheology modifiers, static colorants (such as static tints and / or static dyes), dynamic additives (to facilitate electrode reactions), and combinations thereof. A non-limiting class of art-recognized thermal stabilizers is phenols, such as 2,6-ditertiarybutylphenol and compounds containing a 2,6-ditertiarybutylphenol group or moiety. A non-limiting class of art-recognized UV stabilizers is hindered amine light stabilizers (HALS), such as 2,2,6,6-tetramethylpiperidine and compounds containing a 2,2,6,6-tetramethylpiperidine group or moiety. Static colorants include colorants whose absorption spectrum does not change in response to the application of actinic radiation (such as UV and / or visible light) or an electric potential, and do not include photochromic and electrochromic compounds. Non-limiting classes of kinetic additives include alkali and alkaline earth metal salts of perchlorates, tetrafluoroborates, and hexafluorophosphates; and salts such as tetraalkylammonium salts. Non-limiting examples of rheology modifiers include dialkoxyacetophenones, such as 3',4'dimethoxyacetophenone; and optionally substituted cycloalkylarylketones, such as 1-hydroxycyclohexylphenylketone. Each optional additive can be present in any suitable active amount (e.g., 0.05% to 5% by weight) based on the total solids weight (including the weight of any optional additive) of the electrochromic layer.

[0106] The electrochromic layer of the electrochromic device of the present invention can have any suitable thickness, hi some embodiments, the electrochromic layer has a thickness of from 50 micrometers to 800 micrometers.

[0107] According to some embodiments of the present invention, an electrochromic device includes (a) a first substrate having a surface with a first transparent electrode layer, (b) a second substrate having a surface with a second transparent conductive electrode layer, the first transparent electrode layer and the second transparent electrode layer being spaced apart from each other in opposing directions, and (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer. The electrochromic layer, in this embodiment, includes (i) an electrochromic material comprising a cathodic component having a cationic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having a covalently bonded anion, (ii) an optional electrolyte, and (iii) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - is independently an anion represented by formula (A) previously described herein; and a polymer matrix.

[0108] The cathodic material of the electrochromic material, in some embodiments, is as previously described herein with reference to formulas (III) and (IV).

[0109] In some embodiments, each counteranion of a cathodic component, which is an anodic component to which an anion is covalently attached, is as described herein above with reference to formulas (I) and (II).

[0110] In some embodiments, the cathodic component having a cationic charge and the cathodic component having a covalently bound anion have a net neutral charge together. As used herein, "net neutral charge" with respect to the cathodic component having a cathodic charge and the cathodic component having a covalently bound anion means that the sum of the cathodic charge (+) of the cathodic component and the sum of the anionic charge (-) of the cathodic component having a covalently bound anion are equal to each other (or have the same absolute value). According to some embodiments, the cathodic component having a cathodic charge does not contain any other or additional counter anions other than the cathodic component having a covalently bound anion. Correspondingly, in some embodiments, the cathodic component having a covalently bound anion does not contain any other or additional counter cations other than the cathodic component having a cathodic charge.

[0111] In some embodiments of the present invention, by way of non-limiting example, a cathodic component having a cationic charge as represented by formula (III) and an anodic component having an anion covalently attached thereto may be represented by the following formula (V): [ka] It can be expressed as:

[0112] With respect to formula (V), R 4 and R 5 are each independently as defined herein above with respect to formula (III), and each AA - (Anode anion) is independently selected from anode components having covalently attached anions represented by Formula (I) or Formula (II) previously described herein.

[0113] In some embodiments of the present invention, by way of non-limiting example, a cathodic component having a cationic charge as represented by formula (IV) and an anodic component having an anion covalently attached thereto may be represented by the following formula (VI): [ka] It can be expressed as:

[0114] With respect to formula (VI), R 6 , R 8 , and R 7 are each independently as defined herein above with respect to formula (IV), and each AA - (Anode anion) is independently selected from anode components having covalently attached anions represented by Formula (I) or Formula (II) previously described herein.

[0115] Charge neutral combinations of cathodic components bearing a cationic charge and anodic components having covalently bound anions can be prepared according to the non-limiting preliminary illustrations provided further in the examples herein.

[0116] In the electrochromic device of the present invention, the electrochromic material comprises a cathodic component having a cathodic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having a covalently bound anion, the optional electrolyte being as previously described herein, and poly(diallyldimethylammonium x - The polymer matrix comprising the hydroxyl group is as previously described herein.

[0117] In some embodiments of the present invention, poly(diallyldimethylammonium x) as previously described herein may be used. - In addition to the above, the polymer matrix may include a further polymer, such as 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).

[0118] The electrochromic layer of the electrochromic device of the present invention, in some embodiments, can further include one or more optional art-recognized additives, as previously described herein.

[0119] For non-limiting illustrative purposes, an electrochromic device (3) according to the present invention is shown in FIG. 1. The electrochromic device (3) comprises a first substrate (11) having a first surface (14) and a second surface (17). The first surface (14) of the first substrate (11) comprises a first transparent electrode layer (20) that is electrically conductive. The first transparent electrode layer (20) is present on at least a portion of the first surface (14) of the first substrate (11). In some embodiments, the first transparent electrode layer (20) has the form of one or more patterns (e.g., one or more designs and / or labels) on the first surface (14) of the first substrate (11). In some further embodiments, the first transparent electrode layer (20) forms a substantially continuous layer on the first surface (14) of the first substrate (11). The first transparent electrode layer (20) is in electrical contact with at least one first conductor (21), which in some embodiments may be a first conductive wire.

[0120] The electrochromic element (3) comprises a second substrate (23) having a first surface (26) and a second surface (29). The first surface (26) of the second substrate (23) has a second transparent electrode layer (32) that is electrically conductive. The second transparent electrode layer (32) is present on at least a portion of the first surface (26) of the second substrate (23). In some embodiments, the second transparent electrode layer (32) has the form of one or more patterns (e.g., one or more designs and / or signs) on the first surface (26) of the second substrate (23). In some further embodiments, the second transparent electrode layer (32) forms a substantially continuous layer on the first surface (26) of the second substrate (23). The second transparent electrode layer (32) is in electrical contact with at least one second conductor (33), which in some embodiments may be a second electrically conductive second wire.

[0121] With further reference to the electrochromic element (3) of FIG. 1, the first transparent electrode layer (20) and the second transparent electrode layer (32) face each other in a spaced apart relationship.

[0122] The electrochromic element (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 in abutting relationship between the first transparent electrode layer (20) and the second transparent electrode layer (32).

[0123] The first and second substrates of the electrochromic device are, in some embodiments of the present invention, independently selected from transparent substrates. The transparent substrates from which the first and second substrates can be independently selected are, in some embodiments, made from 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 substrates from which the first and second substrates can be independently selected are made from materials including silica glass. The first and second substrates can, independently, have any suitable thickness. In some embodiments, the first and second substrates, independently, have a thickness of 1 mm to 25 mm, or 2 mm to 10 mm.

[0124] The first and second transparent electrode layers of the electrochromic device of the present invention, in some embodiments, comprise conductive inorganic oxides, conductive organic materials, conductive metals, and / or conductive carbon, such as carboxyl nanotubes and / or graphene. Examples of conductive inorganic oxides include, but are not limited to, tin oxide, which may be doped with a doping material such as indium; zinc oxide, which may further include, for example, aluminum. Examples of conductive organic materials include, but are not limited to, poly(3,4-ethylenedioxythiophene), poly(4,4-dioctylcyclopentadithiophene), and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). The first and second transparent electrode layers, in some embodiments, may each independently be in the form of a grid of metal wires, a grid of carboxyl nanotubes, and / or a layer of graphene. In some embodiments, the first and second transparent electrode layers are each independently selected from semitransparent metal layers. In some further embodiments, one of the first and second transparent electrode layers includes (or is associated with) a reflective metal layer (e.g., including aluminum, gold, and / or silver) and the electrochromic element is a reflective electrochromic element, such as a controllable reflective mirror.

[0125] According to some embodiments, the first and second electrode layers of the electrochromic device of the present invention each independently comprise a conductive material selected from indium tin oxide, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), or a combination thereof.

[0126] The first and second electrode layers of the electrochromic device, according to some embodiments of the present invention, can each independently have any suitable thickness, provided that they are both 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 from 0.01 micrometers to 10 micrometers.

[0127] Examples of articles, such as products, that may include or be defined by the electrochromic elements of the present invention include, but are not limited to, energy efficient and / or privacy transparent films (or windows), e.g., architectural and transportation transparent films or windows; mirrors, e.g., rearview mirrors; optical filters; ophthalmic articles, e.g., corrective lenses, non-corrective lenses, magnifying lenses, protective lenses, and visors; and any other article or application where variable and controllable light transmission and / or color is desired.

[0128] The present invention also provides a polymeric thickener comprising: (i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; and (iv) a polymer, the polymer being poly(diallyldimethylammonium xylene). - ), each X - independently relates to an electrochromic composition comprising a polymeric thickener, which is an anion represented by formula (A) as previously described herein; and (v) a solvent.

[0129] The cathodic component of the electrochromic composition is as previously described herein, such as with respect to formulas (III) and (IV). The cathodic component of the electrochromic composition, in some embodiments, includes a counter anion, and each counter anion of the cathodic component is BF 4 - , P.F. 6 - , ClO 4 - , C.F. 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , and B(phenyl) 4 - is selected from.

[0130] The anode component of the electrochromic composition is as previously described herein, for example, but not limited to, as previously described with reference to formulas (I) and (II). The anode component of the electrochromic composition may, in some embodiments, be a counter cation that may be selected from the classes and examples previously described herein, for example, but not limited to, an alkali metal cation; an alkaline earth metal cation; an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation; an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation; and a tetrasubstituted ammonium cation, such as those described with reference to formula (D), for example, a tetra(straight or branched chain C 1 ~C 10 alkyl)ammonium cation.

[0131] The electrolyte of the electrochromic composition, in some embodiments, is as previously described herein with respect to the electrochromic device of the present invention, etc.

[0132] The polymer of the polymer thickener of the electrochromic composition of the present invention is poly(diallyldimethylammonium x - ), each X - are independently anions represented by formula (A) as previously described herein. In some embodiments, poly(diallyldimethylammonium X - In addition to the above, the polymer thickener may comprise a further polymer, such as 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).

[0133] The electrochromic composition of the present invention includes a solvent. In some embodiments, the solvent of the electrochromic composition is ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C 2 ~C 8 ) dinitrile, or di(linear or branched C 1 ~C 8 ) acetamide.

[0134] The present invention also provides a polymeric thickener comprising: (i) a cathode component having a cationic charge, the cathode component further comprising a counter anion, each counter anion of the cathode component being an anode component having a covalently bound anion; (ii) an optional electrolyte; and (iii) a polymeric thickener comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - independently relates to an electrochromic composition comprising a polymeric thickener, which is an anion represented by formula (A) previously described herein; and (iv) a solvent.

[0135] The electrolyte of the electrochromic composition of the present invention, the polymer of the polymeric thickener, and the solvent are each as previously described herein.

[0136] A cathodic component having a cationic charge and further comprising a counteranion, each counteranion of the cathodic component being an anodic component having an anion covalently bound thereto, the cathodic component being as hereinbefore described, such as with reference to Formulas (V) and (VI).

[0137] The cathodic component of the electrochromic composition having a cationic charge is as previously described herein with reference to Formulas (III) and (IV), etc. The anodic component of the electrochromic composition having a covalently bound anion is as previously described herein with reference to Formulas (I) and (II), etc.

[0138] In some embodiments of the electrochromic composition, the cathodic component having a cationic charge and the anodic component having a covalently bound anion have a net neutral charge together. The term "net neutral charge" with respect to the cathodic component having a cationic charge and the anodic component having a covalently bound anion is as described hereinabove. According to some embodiments of the electrochromic composition, the cathodic component having a cationic charge does not contain any other or additional counter anion other than the anodic component having a covalently bound anion. Correspondingly, in some embodiments of the electrochromic composition, the anodic component having a covalently bound anion does not contain any other or additional counter cation other than the cathodic component having a cationic charge.

[0139] The cathodic component having a cationic charge, in some embodiments, is present in the electrochromic composition in an amount of 0.25 wt % to 6.25 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 3 wt %, where the wt % in each case is based on the total weight of the electrochromic composition.

[0140] Anode components, including but not limited to, anode components having covalently bound anions, are present in the electrochromic composition in an amount of from 0.25 wt % to 6.25 wt %, or from 0.5 wt % to 5 wt %, or from 1 wt % to 3 wt %, in some embodiments, where the weight percentage in each case is based on the total weight of the electrochromic composition.

[0141] The electrolyte is present in the electrochromic composition in an amount of from 1 wt % to 75 wt %, or from 5 wt % to 50 wt %, or from 10 wt % to 30 wt %, in some embodiments, where the weight percentage in each case is based on the total weight of the electrochromic composition.

[0142] The polymeric thickener is present in the electrochromic composition in an amount of from 5% to 80% by weight, or from 10% to 60% by weight, or from 15% to 50% by weight, in some embodiments, where the weight percentages in each case are based on the total weight of the electrochromic composition.

[0143] The solvent is present in the electrochromic composition in an amount of from 10 to 75 weight percent, or from 20 to 60 weight percent, or from 25 to 50 weight percent, in some embodiments, where the weight percent in each case is based on the total weight of the electrochromic composition.

[0144] The electrochromic compositions of the present invention, in some embodiments, can include one or more art-recognized optional additives, such as, but not limited to, thermal stabilizers, UV stabilizers, rheology modifiers, static colorants (such as static tints and / or static dyes), dynamic additives (to facilitate electrode reactions), and combinations thereof. The optional additives, in each case, are as previously described herein with respect to the electrochromic devices of the present invention. Each optional additive can be present in the electrochromic composition in any suitable active amount, for example, 0.05% to 5% by weight, based on the total weight of the electrochromic composition including the weight of the optional additive.

[0145] 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 electrochromic layer includes the following steps: First, all components of the electrochromic composition (except the polymer thickener) are mixed under shear (e.g., with an impeller) until a homogenous mixture is formed. Second, the polymer thickener is added and mixed to form a viscous paste. The viscous paste is compounded at high temperature and extruded into a desired form such as a film (in some embodiments, this can be accomplished by a heated extrusion screw and slot die). This film can be deposited on a sacrificial or temporary liner (e.g., in some embodiments, composed of polyethylene terephthalate) or can be extruded directly onto the first transparent electrode layer of the first substrate. In embodiments using a sacrificial liner, the film / electrochromic layer is then separated from the sacrificial / temporary liner (which is discarded), cut to size as needed, and placed above or on the first transparent electrode layer of the first substrate. The second transparent electrode of the second substrate is disposed on or over the other (or facing / exposed) side of the electrochromic layer to form a stack including the first substrate, the first transparent electrode, the electrochromic layer, the second transparent electrode, and the second substrate. The stack can optionally further include an electrical connector that electrically contacts the first and second transparent electrodes separately. The stack (with any gasket surrounding at least the outer edge of the electrochromic layer) is subjected to vacuum lamination while simultaneously applying an elevated temperature, such as 110° C. to 200° C., for a period of time, such as 10 to 30 minutes. After cooling, the electrochromic device so formed is removed from the vacuum laminated device.

[0146] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0147] Clause 1:(a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface provided with a second transparent conductive electrode layer, The first transparent electrode layer and the second transparent electrode layer are opposed to each other with a space therebetween. A second substrate; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; (iv) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - are independently expressed by the following formula (A): [ka] (In the formula, R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. a polymer matrix, the anion being represented by an electrochromic layer comprising An electrochromic element comprising:

[0148] Clause 2: For formula (A), R 9 and R 10 each independently represents fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 2. The electrochromic device of claim 1, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0149] Clause 3: For formula (A), R 9 and R 10 each independently represents a linear or branched chain C 1 ~C 53. The electrochromic device of claim 1 or 2, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0150] Clause 4: For formula (A), R 9 and R 10 4. The electrochromic device of any one of clauses 1, 2, or 3, wherein each of the isopropyl groups is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

[0151] Clause 5: The anode component is represented by the following formula (I) or formula (II): [ka] (For formula (I), R 1 is selected from divalent linear or branched alkane linking groups; With respect to formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. 5. The electrochromic device of any one of clauses 1, 2, 3, or 4, comprising at least one anode component anion selected from the group consisting of:

[0152] Clause 6: With respect to formula (I), R 1 is a divalent linear or branched C 1 ~C 10 alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 10 alkane linking groups; R 3 Fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 106. The electrochromic device of claim 5, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0153] Clause 7: For formula (I), R 1 is a divalent linear or branched C 1 ~C 5 alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 5 alkane linking groups; R 3 is a straight or branched chain 1 ~C 5 7. The electrochromic device according to claim 5 or 6, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0154] Clause 8: The electrochromic device of any one of clauses 5, 6, or 7, wherein the anode component further comprises a counter cation.

[0155] Clause 9: The electrochromic device of clause 8, wherein each countercation is independently selected from an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation, an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation, a tetrasubstituted ammonium cation, or a combination thereof.

[0156] Clause 10: Each counter cation has the following formula (B): [ka] (In the formula, R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl. 10. The electrochromic device according to claim 8 or 9, wherein the tetrasubstituted ammonium cation is selected from the group consisting of tetrasubstituted ammonium cations represented by

[0157] Article 11:R a , Rb , R c and R d each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 11. The electrochromic device of claim 10, wherein the alkyl group is selected from cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0158] Article 12:R a , R b , R c and R d each independently represents a linear or branched chain C 1 ~C 10 12. The electrochromic device according to claim 10 or 11, wherein the alkyl is selected from the group consisting of aryl, aryl, aryl and alkyl.

[0159] Clause 13: The electrochromic device of any one of clauses 8, 9, 10, 11, or 12, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0160] Clause 14: Each countercation is independently a tetra (linear or branched C 1 ~C 10 14. The electrochromic device of any one of clauses 8, 9, 10, 11, 12, or 13, wherein the cation is selected from the group consisting of alkyl)ammonium cations.

[0161] Clause 15: The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): [ka] (For formula (III), R 4 and R 5 each independently represents a linear or branched chain C1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 selected from cycloalkyl, unsubstituted aryl, and substituted aryl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C 1 ~C 10 alkane linking groups) 15. The electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, comprising at least one of:

[0162] Clause 16: With respect to formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 4 selected from alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 4 R is selected from alkyl, unsubstituted phenyl, and substituted phenyl; 7 is a divalent linear or branched C 1 ~C 8 16. The electrochromic device of clause 15, wherein the linking group is selected from the group consisting of alkane linking groups.

[0163] Clause 17. The cathodic component further comprises a counter anion, each counter anion of the cathodic component being BF 4 - , P.F. 6- , ClO 4 - , C.F. 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , and B(phenyl) 4 - 17. The electrochromic device according to claim 15 or 16, selected from the group consisting of:

[0164] Clause 18: The electrolyte is present; At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched chain C 1 ~C 6 at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C 1 ~C 6 Alkyl)-3-(straight or branched C 1 ~C 6 Alkyl)imidazolium, 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 alkyl) piperidinium, phosphonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)phosphonium or tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 alkyl)phosphonium or ammonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)ammonium, and tri(C 5 ~C8 Cycloalkyl)-(linear or branched C 1 ~C 6 At least one electrolyte cation selected from the group consisting of alkyl (alkyl) ammonium; 18. The electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, comprising:

[0165] Clause 19: The polymer matrix comprises a further polymer, the further polymer being selected from the group consisting 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 19. The electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18, comprising at least one of:

[0166] Clause 20:(a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface provided with a second transparent conductive electrode layer, The first transparent electrode layer and the second transparent electrode layer are opposed to each other with a space therebetween. A second substrate; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) an electrochromic material comprising a cathodic component having a cathodic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having an anion covalently bonded thereto; (ii) an optional electrolyte; (iii) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X- are independently expressed by the following formula (A): [ka] (In the formula, R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. a polymer matrix, the anion being represented by an electrochromic layer comprising An electrochromic element comprising:

[0167] Clause 21: For formula (A), R 9 and R 10 each independently represents fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 21. The electrochromic device of claim 20, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0168] Clause 22: For formula (A), R 9 and R 10 each independently represents a linear or branched chain C 1 ~C 5 22. The electrochromic device according to claim 20 or 21, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0169] Clause 23: For formula (A), R 9 and R 10 23. The electrochromic device of any one of clauses 20, 21, or 22, wherein each of the isopropyl groups is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

[0170] Clause 24: An electrochromic device according to any one of clauses 20, 21, 22 or 23, wherein the cathodic component having a cationic charge and the anodic component to which the anion is covalently bound have a combined net neutral charge.

[0171] Clause 25: The anode component to which an anion is covalently bound is represented by the following formula (I) or formula (II): [ka] (For formula (I), R 1 is selected from divalent linear or branched alkane linking groups; With respect to formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. 25. The electrochromic device of any one of clauses 20, 21, 22, 23, or 24, wherein the anode component is selected from the anode components represented by at least one of:

[0172] Clause 26: With respect to formula (I), R 1 is a divalent linear or branched C 1 ~C 10 alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 10 alkane linking groups; R 3 Fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 22. The electrochromic device of claim 21, wherein the alkyl group is selected from perfluorinated alkyl groups.

[0173] Clause 27: The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): [ka] (For formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 selected from cycloalkyl, unsubstituted aryl, and substituted aryl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C 1 ~C 10 alkane linking groups) 27. The electrochromic device of any one of clauses 20, 21, 22, 23, 24, 25, or 26, comprising at least one of:

[0174] Clause 28: With respect to formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 4 selected from alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C4 R is selected from alkyl, unsubstituted phenyl, and substituted phenyl; 7 is a divalent linear or branched C 1 ~C 8 28. The electrochromic device of clause 27, wherein the linking group is selected from the group consisting of alkane linking groups.

[0175] Clause 29: The electrolyte is present; At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched chain C 1 ~C 6 at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C 1 ~C 6 Alkyl)-3-(straight or branched C 1 ~C 6 Alkyl)imidazolium, 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 alkyl) piperidinium, phosphonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)phosphonium or tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 alkyl)phosphonium or ammonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)ammonium, and tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 At least one electrolyte cation selected from the group consisting of alkyl (alkyl) ammonium; 30. The electrochromic device of any one of clauses 20, 21, 22, 23, 24, 25, 26, 27, or 28, comprising:

[0176] Clause 30: The polymer matrix further comprises an additional polymer, the additional polymer being selected from the group consisting 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 30. The electrochromic device of any one of clauses 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29, further comprising at least one of:

[0177] Clause 31:(i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; (iv) a polymeric thickener comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - are independently expressed by the following formula (A): [ka] (In the formula, R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. and a polymeric thickener, the anion of which is represented by (v) a solvent; 1. An electrochromic composition comprising:

[0178] Clause 32: For formula (A), R 9 and R 10 each independently represents fluorine, linear or branched C 1 ~C 10Fluorinated alkyl or linear or branched C 1 ~C 10 32. The electrochromic composition of claim 31, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0179] Clause 33: For formula (A), R 9 and R 10 each independently represents a linear or branched chain C 1 ~C 5 33. The electrochromic composition of claim 32, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0180] Clause 34: For formula (A), R 9 and R 10 34. The electrochromic composition of any one of clauses 31, 32, or 33, wherein each of the isopropyl groups is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

[0181] Clause 35: The anode component is represented by the following formula (I) or formula (II): [ka] (For formula (I), R 1 is selected from divalent linear or branched alkane linking groups; With respect to formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. 35. The electrochromic composition of any one of clauses 31, 32, 33, or 34, comprising at least one anodic component anion selected from the group consisting of:

[0182] Clause 36: With respect to formula (I), R 1 is a divalent linear or branched C 1 ~C 10alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 10 alkane linking groups; R 3 Fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 36. The electrochromic composition of claim 35, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0183] Clause 37: For formula (I), R 1 is a divalent linear or branched C 1 ~C 5 alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 5 alkane linking groups; R 3 is a straight or branched chain 1 ~C 5 37. The electrochromic composition of claim 35 or 36, wherein the alkyl group is selected from perfluorinated alkyl groups.

[0184] Clause 38: The electrochromic composition of any one of clauses 31, 32, 33, 34, 35, 36, or 37, wherein the anodic component further comprises a counter cation.

[0185] Clause 39: The electrochromic composition of clause 38, wherein each countercation is independently selected from an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation, an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation, a tetrasubstituted ammonium cation, or a combination thereof.

[0186] Clause 40: each counter cation is represented by the following formula (B): [ka] (In the formula, Ra , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl. 40. The electrochromic composition according to claim 38 or 39, wherein the tetrasubstituted ammonium cation is selected from those represented by

[0187] Article 41:R a , R b , R c and R d each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 41. The electrochromic composition of claim 40, wherein the alkyl group is selected from cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0188] Article 42:R a , R b , R c and R d each independently represents a linear or branched chain C 1 ~C 10 42. The electrochromic composition according to claim 40 or 41, wherein the alkyl is selected from the group consisting of aryl, ... and alkyl.

[0189] Clause 43: The electrochromic composition of any one of clauses 38, 39, 40, 41, or 42, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0190] Clause 44: Each countercation is independently a tetra (linear or branched C 1 ~C 10 44. The electrochromic composition of any one of clauses 38, 39, 40, 41, 42, or 43, wherein the cation is selected from the group consisting of alkyl, aryl ...

[0191] Clause 45: The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): [ka] (For formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 selected from cycloalkyl, unsubstituted aryl, and substituted aryl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C 1 ~C 10 alkane linking groups) 45. The electrochromic composition of any one of clauses 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, or 44, comprising at least one of:

[0192] Clause 46: With respect to formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 4 selected from alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8each independently represents a linear or branched chain C 1 ~C 4 R is selected from alkyl, unsubstituted phenyl, and substituted phenyl; 7 is a divalent linear or branched C 1 ~C 8 46. ​​The electrochromic composition of claim 45, wherein the linking group is selected from the group consisting of alkane linking groups.

[0193] Clause 47. The cathodic component further comprises a counter anion, each counter anion of the cathodic component being BF 4 - , P.F. 6 - , ClO 4 - , C.F. 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , and B(phenyl) 4 - 47. The electrochromic composition according to claim 45 or 46, selected from the group consisting of:

[0194] Clause 48: The electrolyte is present; At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched chain C 1 ~C 6 at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C 1 ~C 6 Alkyl)-3-(straight or branched C 1 ~C 6 alkyl)imidazolium, or 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6At least one electrolyte cation selected from the group consisting of alkyl) piperidinium; 48. The electrochromic composition of any one of clauses 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, or 47, comprising:

[0195] Clause 49: The polymer matrix comprises a further polymer, the further polymer being selected from the group consisting 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 50. The electrochromic composition of any one of clauses 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, or 48, comprising at least one of:

[0196] Clause 50: (i) a cathodic component having a cathodic charge, said cathodic component further comprising a counter anion, each counter anion of said cathodic component being an anodic component having an anion covalently bound thereto; (ii) an optional electrolyte; (iii) a polymeric thickener comprising a polymer, the polymer being poly(diallyldimethylammonium X - ), each X - are independently expressed by the following formula (A): [ka] (In the formula, R 9 and R 10 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. and a polymeric thickener, the anion of which is represented by (iv) a solvent; 1. An electrochromic composition comprising:

[0197] Clause 51: For formula (A), R 9 and R 10 each independently represents fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 51. The electrochromic composition of claim 50, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0198] Clause 52: For formula (A), R 9 and R 10 each independently represents a linear or branched chain C 1 ~C 5 52. The electrochromic composition of claim 50 or 51, wherein the alkyl group is selected from perfluorinated alkyl groups.

[0199] Clause 53: For formula (A), R 9 and R 10 53. The electrochromic composition of any one of clauses 50, 51, or 52, wherein each of the isopropyl groups is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

[0200] Clause 54: The electrochromic composition of any one of clauses 50, 51, 52, or 53, wherein the cathodic component having a cationic charge and the anodic component to which the anion is covalently bound have a combined net neutral charge.

[0201] Clause 55: The anode component to which an anion is covalently bound is represented by the following formula (I) or formula (II): [ka] (For formula (I), R 1 is selected from divalent linear or branched alkane linking groups; With respect to formula (II), R 2is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. 55. The electrochromic composition of any one of clauses 50, 51, 52, 53, or 54, wherein the anodic component is selected from the anodic components represented by at least one of:

[0202] Clause 56: With respect to formula (I), R 1 is a divalent linear or branched C 1 ~C 10 alkane linking groups, With respect to formula (II), R 2 is a divalent linear or branched C 1 ~C 10 alkane linking groups; R 3 Fluorine, linear or branched C 1 ~C 10 Fluorinated alkyl or linear or branched C 1 ~C 10 56. The electrochromic composition of claim 55, wherein the alkyl group is selected from the group consisting of perfluorinated alkyl groups.

[0203] Clause 57: The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): [ka] (For formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 selected from cycloalkyl, unsubstituted aryl, and substituted aryl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 10 Alkyl, unsubstituted C 3 ~C 7 Cycloalkyl, substituted C 3 ~C 7 is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C 1 ~C 10 alkane linking groups) 57. The electrochromic composition of any one of clauses 50, 51, 52, 53, 54, 55, or 56, comprising at least one of:

[0204] Clause 58: With respect to formula (III), R 4 and R 5 each independently represents a linear or branched chain C 1 ~C 4 selected from alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8 each independently represents a linear or branched chain C 1 ~C 4 R is selected from alkyl, unsubstituted phenyl, and substituted phenyl; 7 is a divalent linear or branched C 1 ~C 8 58. The electrochromic composition of claim 57, wherein the linking group is selected from the group consisting of alkane linking groups.

[0205] Clause 59: The electrolyte is present, At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched chain C 1 ~C 6 at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C 1 ~C 6Alkyl)-3-(straight or branched C 1 ~C 6 Alkyl)imidazolium, 1-(linear or branched C 1 ~C 6 Alkyl)-1-(straight or branched C 1 ~C 6 alkyl) piperidinium, phosphonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)phosphonium or tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 alkyl)phosphonium or ammonium cations, such as, but not limited to, tetra(linear or branched C 1 ~C 6 alkyl)ammonium, and tri(C 5 ~C 8 Cycloalkyl)-(linear or branched C 1 ~C 6 At least one electrolyte cation selected from the group consisting of alkyl (alkyl) ammonium; 59. The electrochromic composition of any one of clauses 50, 51, 52, 53, 54, 55, 56, 57, or 58, comprising:

[0206] Clause 60: The polymer matrix further comprises an additional polymer, the additional polymer being selected from the group consisting 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 60. The electrochromic composition of any one of clauses 50, 51, 52, 53, 54, 55, 56, 57, 58, or 59, comprising at least one of:

[0207] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations will be apparent to those skilled in the art.

[0208] example Part 1 of the examples describes the synthesis of an anodic component with a covalently bound anion according to the invention. Part 2 describes the synthesis of a cathodic component with a cationic charge, the respective counter anion of which is an anodic component with a covalently bound anion according to the invention. Part 3 describes the synthesis of poly(diallyldimethylammonium X) according to the invention. - Part 2 describes the preparation of an electrochromic device according to the invention. Part 3 describes the preparation of an electrochromic device according to the invention. Part 4 describes the evaluation of the electrochromic device according to Part 3.

[0209] Part 1 Synthesis Example 1 With reference to the following scheme (1), 1 A non-limiting illustration of the preparation of an anion-covalently attached anode component according to the present invention is provided, represented by the formula:

[0210] To an oven-dried 500 ml three-neck round bottom flask with magnetic stirring was added 200 mL of dimethylformamide (DMF) and 10 g of (1) phenothiazine (50.2 mmol). The solution was stirred for 1 hour with nitrogen purge. To the reaction mixture was added 2.4 g of 60% NaH (60 mmol). The solution was observed to turn deep red as gas bubbles were generated therefrom. After 1 hour of continuous mixing under nitrogen, the generation of gas bubbles was observed to cease. Under a nitrogen sweep, 6.6 g of (2) 1,3-propane sultone (55.2 mmol) dissolved in 10 g of dry DMF was added dropwise to the contents of the flask. After the addition of (2) 1,3-propane sultone was completed, the reaction mixture was left stirring at room temperature under nitrogen for 18 hours.

[0211] The reaction was quenched by adding 100 mL of deionized (DI) water and the solvent was removed by applying a vacuum, after which an oil remained in the flask. 50 mL of ethyl acetate was added to the oil, forming a precipitate which was collected by vacuum filtration. The precipitate was washed with cold ethyl acetate and dried overnight under vacuum at 60° C. to give the desired product (3) sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate as an off-white solid. [ka]

[0212] Synthesis Example 2 With reference to the following scheme (2), 2 is a divalent n-propane linking group, R 3 A non-limiting illustration of the preparation of an anion-covalently bound anodic component according to the present invention is provided, represented by the formula:

[0213] (3) Sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was prepared according to Synthesis Example 1. One gram (0.0029 mol) of (3) sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was finely ground in a mortar and pestle, then cooled to 100° C. with a magnetic stir bar and N 2 A 100 ml round bottom flask equipped with a reflux condenser equipped with a sweep / blanket was placed in the flask. A 20 ml quantity of acetone and 40 mg of 18-crown-6 ether were added to the flask and the mixture was stirred vigorously for 15 min. The solution became cloudy, but the presence of solid sodium salt (3) was observed. (4) Cyanuric chloride (540 mg, 0.0029 mol, 1 equiv.) was dissolved in N 2The mixture was refluxed in an oil bath (ca. 80° C.) for 24 h. The solution turned orange in color and a fine precipitate formed. Large chunks of the initial Na salt (3) were no longer observable. Thin layer chromatography (TLC) showed the presence of a single reaction product that turned pink upon exposure to shortwave (316 nm) UV in air, proving the formation of (5) 3-(10H-phenothiazin-10-yl)-propane-1-sulfonyl chloride. The product (5) was fairly mobile in 50:50 EtOAc / hexanes. The reaction mixture was cooled to room temperature and filtered through a thin layer of alumina. The solvent was removed under vacuum to give 1.25 g of an orange-yellow glassy solid (5). The product (5) was dissolved in MeCN and the solid was filtered off. The filtrate was used in the next step without further purification.

[0214] (6) Trifluoromethylsulfonamide (4.53 g, 0.0305 mol, 1.05 equiv.) and potassium carbonate (40 g, 0.29 mol, 10 equiv.) were placed in a 500 ml three-neck flask equipped with a reflux condenser, a magnetic stir bar, and a fritted Schlenk funnel. A nitrogen supply was attached to the condenser and Schlenk funnel and secured with plastic clips. A strong nitrogen flux was used to flush the vessel for 15 s, and a septum was placed on the remaining neck. An amount of 100 ml of anhydrous MeCN was added through the septum using a syringe. The mixture was stirred vigorously for 20 min, resulting in a white cloudy dispersion. To the crude (5) 3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride (9.84 g, 0.029 mol) (filtrate from previous step) was added 50 ml of dry MeCN under nitrogen flow and the resulting solution was transferred to a fritted Schlenk funnel. The Schlenk funnel was purged with nitrogen and stoppered with a clip. The solution of MeCN and (5) 3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride was added dropwise to the three-neck flask at room temperature over 1 hour. The contents of the three-neck flask were refluxed for 24 hours. The formation of a coarse precipitate was observed. The precipitate was filtered off and the resulting solution was concentrated under vacuum. The residue was recrystallized from water to give the product (7) potassium 3-(10H-phenothiazin-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonamide in the form of brown needles. [ka]

[0215] Part 2 With reference to Scheme (3) below, a non-limiting illustration of the preparation of the cathode component (9) 1,1'-diheptyl-[4,4'-bipyridine]-1,1'-diium-bis-[3-(10H-phenothiazin-10-yl)propane-1-sulfonate according to the present invention is provided. With further reference to Scheme (3) below, for compounds (8) and (9), R 4 and R 5 is heptyl in both cases.

[0216] To a 200 mL Erlenmeyer flask was added 2 g of (8) 1,1'-diheptyl-[4,4'-bipyridine]-1,1'-diium dibromide (3.89 mmol) and 50 mL of deionized (DI) water with magnetic stirring. The mixture was stirred until a solution was formed. With further stirring, 2.8 g of (3) sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate (8.16 mmol / 2.1 eq) in 50 mL of water was added. A dark purple precipitate formed immediately. The reaction mixture was stirred for 3 h. The precipitate was collected by vacuum filtration, washed several times with water, and dried overnight under vacuum at 60° C. to give the product (9) 1,1′-diheptyl-[4,4′-bipyridine]-1,1′-diium-bis-[3-(10H-phenothiazin-10-yl)propane-1-sulfonate in the form of dark purple crystals. [ka]

[0217] Part 3 With reference to the following scheme (4), and with reference to formula (A) provided hereinabove, poly(diallyldimethylammonium X - A non-limiting description of the preparation of a polymer is provided, where R 9 and R 10 are trifluoromethyl).

[0218] To a 2-liter, two-necked, round-bottom flask equipped with a mechanical stirrer was added 95 g of (11) lithium bis(trifluoromethane)sulfonimide and 300 ml of deionized water. The contents of the flask were then stirred at 500 rpm and heated to and held at 80°C. While the contents of the flask were maintained at 80°C, 250 g of (10) poly(diallyldimethylammonium chloride) 20 wt% in water (commercially available from Sigma-Aldrich, reported Mw of 400-500 kDa) was added dropwise over a 10-minute period (310 mmol of chloride). The contents of the flask were stirred vigorously at 800 rpm for 18 hours and then cooled to ambient room temperature, allowing a precipitate to form. The precipitate was collected by vacuum filtration and washed several times with deionized water.

[0219] The collected and washed precipitate, 500 ml of deionized water, and 10 g of (11) lithium bis(trifluoromethane)sulfonimide were added to a 2-liter, two-necked round-bottom flask equipped with a mechanical stirrer. With stirring at 800 rpm, the contents of the flask were heated to 80° C. and held for 18 hours, then cooled to ambient room temperature to form a precipitate. The precipitate was collected by vacuum filtration and washed several times with deionized water, followed by several washes with methanol. The washed precipitate was collected, placed in a cellulose thimble, and subjected to Soxhlet extraction with methanol for 24 hours. The solvent was switched to acetone to collect the desired fraction. The solvent was removed under vacuum, and the resulting powder was dried under vacuum to give 110.9 g of (12) poly((diallyldimethylammonium bis(trifluoromethane)sulfonimide)) in about 88% yield. [ka]

[0220] Part 4 The preparation of an electrochromic device according to the invention is described below: An initial solution was prepared with magnetic stirring from sulfolane (5 g), 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonimide (EMIM-TFSI) (1 g), potassium 3-(10H-phenothiazin-10-yl)-N-triflylpropane-1-sulfonamide (PTTK) (100 mg), and 1,1'-diethyl-4,4'-bipyridinium bis(trifluoromethane)sulfonimide (diethyl viologen TFSI) (100 mg). 5 g of poly((diallyldimethylammonium bis(trifluoromethane)sulfonimide) (PDADMA-TFSI) was added to the initial solution, followed by vigorous mixing at elevated temperature to form a concentrated solution. While still hot, a volumetrically dosed portion of the concentrated solution was drop-cast onto a fluorine-doped tin oxide (FTO) glass electrode (3 in. × 4 in.; 7.62 cm × 10.16 cm) with copper tape wrapped on the edges, which was then covered with insulating polyimide. A prefabricated thermoplastic gasket, 0.5 in. (1.27 cm) wide and 400 microns thick, was added, which surrounded the active area. A second fluorine-doped tin oxide (FTO) glass electrode was placed on top of the electrochromic layer. The stack was vacuum laminated at 140 °C for 15 minutes to completely melt and seal the gasket. After cooling, the so-formed electrochromic device was removed from the vacuum laminated device.

[0221] Part 5 The electrochromic element of Part 4 was placed on top (in front) of a light-colored label containing the indicia (Vitro® Architectural Glass) and subjected to a potential of 1.2 V for 10 minutes. With reference to FIG. 2 of the drawings, a photograph of the electrochromic element of Part 4 in a clear / non-activated state is shown on the left (a). With further reference to FIG. 2, a photograph of the electrochromic element of Part 4 in a dark / activated state (after being subjected to 1.2 V for 10 minutes) is shown on the left (b). As shown in FIG. 2, electrochromic elements according to the present invention can provide a significant and desirable change in visible light transmittance (VLT) in the dark / activated state.

[0222] The invention has been described with reference to specific details of particular embodiments thereof, and it is not intended that such details be considered limitations on the scope of the invention, except to the extent that they are included in the appended claims.

Claims

1. (a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface provided with a second transparent conductive electrode layer, The first transparent electrode layer and the second transparent electrode layer are opposed to each other with a space therebetween. A second substrate; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) a cathode component; (ii) an anode component; and (iii) an optional electrolyte; and (iv) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 1】 (In the formula, R ９ and R １０ are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. a polymer matrix, the anion being represented by an electrochromic layer comprising An electrochromic element comprising:

2. For formula (A), R ９ and R １０ each independently represents fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 2. The electrochromic device of claim 1, wherein the alkyl group is selected from perfluorinated alkyl groups.

3. For formula (A), R ９ and R １０ each independently represents a linear or branched chain C １ ~C ５ 3. The electrochromic device of claim 2, wherein the alkyl group is selected from perfluorinated alkyl groups.

4. For formula (A), R ９ and R １０ 4. The electrochromic device of claim 3, wherein each is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

5. The anode component is represented by the following formula (I) or formula (II): 【Chemistry 2】 (For formula (I), R １ is selected from divalent linear or branched alkane linking groups; For formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

2. The electrochromic device of claim 1, comprising at least one anodic component anion selected from the group consisting of:

6. For formula (I), R １ is a divalent straight or branched chain C １ ~C １０ alkane linking groups, For formula (II), R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 6. The electrochromic device of claim 5, wherein the alkyl group is selected from perfluorinated alkyl groups.

7. For formula (I), R １ is a divalent straight or branched chain C １ ~C ５ alkane linking groups, For formula (II), R ２ is a divalent straight or branched chain C １ ~C ５ alkane linking groups; R ３ is a straight or branched chain １ ~C ５ 7. The electrochromic device of claim 6, wherein the alkyl group is selected from perfluorinated alkyl groups.

8. The electrochromic device of claim 5 , wherein the anodic component further comprises a counter cation.

9. 9. The electrochromic device of claim 8, wherein each countercation is independently selected from tetra(straight or branched chain alkyl)ammonium cations.

10. Each countercation is independently a tetra (linear or branched C １ ~C １０ 10. The electrochromic device of claim 9, wherein the cation is selected from the group consisting of alkyl) ammonium cations.

11. The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III): 【Chemistry 3】 (For formula (III), R ４ and R ５ each independently represents a linear or branched chain C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ selected from cycloalkyl, unsubstituted aryl, and substituted aryl; For formula (IV), R ６ and R ８ each independently represents a linear or branched chain C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R ７ is a divalent linear or branched C １ ~C １０ alkane linking groups) The electrochromic device of claim 1 , comprising at least one of:

12. For formula (III), R ４ and R ５ each independently represents a linear or branched chain C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; For formula (IV), R ６ and R ８ each independently represents a linear or branched chain C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; R ７ is a divalent straight or branched chain C １ ~C ８ 12. The electrochromic device of claim 11, wherein the linking group is selected from alkane linking groups.

13. The cathodic component further comprises a counter anion, each counter anion of the cathodic component being BF ４ － , P.F. ６ － , ClO ４ － , C.F. ３ SO ３ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and B (phenyl) ４ － 12. The electrochromic device of claim 11, selected from the group consisting of:

14. the electrolyte is present, At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched C １ ~C ６ at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C １ ~C ６ Alkyl)-3-(straight or branched C １ ~C ６ alkyl)imidazolium, 1-(linear or branched C １ ~C ６ Alkyl)-1-(straight or branched chain C １ ~C ６ Alkyl) piperidinium, tetra (straight or branched chain C １ ~C ６ alkyl)phosphonium, tri(C ５ ~C ８ Cycloalkyl)-(straight or branched chain C １ ~C ６ Alkyl)phosphonium, tetra(straight or branched chain C １ ~C ６ alkyl)ammonium or tri(C ５ ~C ８ Cycloalkyl)-(straight or branched chain C １ ~C ６ At least one electrolyte cation selected from the group consisting of ammonium, ammonium cations, and The electrochromic device of claim 1 , comprising:

15. The polymer matrix comprises a further polymer, the further polymer being 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 10. The electrochromic device of claim 1 comprising at least one of the following: (alkyl)(meth)acrylate.

16. (a) a first substrate having a surface with a first transparent electrode layer; (b) a second substrate having a surface provided with a second transparent conductive electrode layer, The first transparent electrode layer and the second transparent electrode layer are opposed to each other with a space therebetween. A second substrate; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) an electrochromic material comprising a cathodic component having a cathodic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having an anion covalently bonded thereto; (ii) an optional electrolyte; and (iii) a polymer matrix comprising a polymer, the polymer being poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 4】 (In the formula, R ９ and R １０ are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. a polymer matrix, the anion being represented by an electrochromic layer comprising An electrochromic element comprising:

17. For formula (A), R ９ and R １０ each independently represents fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 17. The electrochromic device of claim 16, wherein the alkyl group is selected from perfluorinated alkyl groups.

18. For formula (A), R ９ and R １０ each independently represents a linear or branched chain C １ ~C ５ 20. The electrochromic device of claim 17, wherein the alkyl group is selected from perfluorinated alkyl groups.

19. For formula (A), R ９ and R １０ 20. The electrochromic device of claim 18, wherein each is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

20. 17. The electrochromic device of claim 16, wherein the cathodic component having a cationic charge and the anodic component to which the anion is covalently bound have a combined net neutral charge.

21. The anodic component having a covalently bound anion is represented by the following formula (I) or (II): 【Chemistry 5】 (For formula (I), R １ is selected from divalent linear or branched alkane linking groups; For formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

17. The electrochromic device of claim 16, wherein the anodic component is selected from the anodic components represented by at least one of:

22. For formula (I), R １ is a divalent linear or branched C １ ~C １０ alkane linking groups, For formula (II), R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 22. The electrochromic device of claim 21, wherein the alkyl group is selected from perfluorinated alkyl groups.

23. The cathode component is a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III): 【Chemistry 6】 (For formula (III), R ４ and R ５ each independently represents a linear or branched chain C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ selected from cycloalkyl, unsubstituted aryl, and substituted aryl; For formula (IV), R ６ and R ８ each independently represents a linear or branched chain C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R ７ is a divalent linear or branched C １ ~C １０ alkane linking groups) 17. The electrochromic device of claim 16, comprising at least one of:

24. For formula (III), R ４ and R ５ each independently represents a linear or branched chain C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; For formula (IV), R ６ and R ８ each independently represents a linear or branched chain C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; R ７ is a divalent linear or branched C １ ~C ８ 24. The electrochromic device of claim 23, wherein the linking group is selected from an alkane linking group.

25. the electrolyte is present, At least one electrolyte anion, each electrolyte anion being independently selected from the group consisting of bis(perfluoro(linear or branched C １ ~C ６ at least one electrolyte anion selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation independently being 1-(linear or branched C １ ~C ６ Alkyl)-3-(straight or branched C １ ~C ６ alkyl)imidazolium, 1-(linear or branched C １ ~C ６ Alkyl)-1-(straight or branched chain C １ ~C ６ Alkyl) piperidinium, tetra (straight or branched chain C １ ~C ６ alkyl)phosphonium, tri(C ５ ~C ８ Cycloalkyl)-(straight or branched chain C １ ~C ６ Alkyl)phosphonium, tetra(straight or branched chain C １ ~C ６ alkyl)ammonium or tri(C ５ ~C ８ Cycloalkyl)-(straight or branched chain C １ ~C ６ At least one electrolyte cation selected from the group consisting of ammonium, ammonium cations, and 17. The electrochromic device of claim 16, comprising:

26. The polymer matrix further comprises an additional polymer, the additional polymer being 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 20. The electrochromic device of claim 16, comprising at least one of the following: (alkyl)(meth)acrylate.

27. (i) a cathode component; (ii) an anode component; and (iii) an optional electrolyte; and (iv) a polymeric thickener comprising a polymer, the polymer being poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 7】 (In the formula, R ９ and R １０ are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. and a polymeric thickener, the anion of which is represented by (v) a solvent; 1. An electrochromic composition comprising:

28. For formula (A), R ９ and R １０ each independently represents fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 28. The electrochromic composition of claim 27, wherein the alkyl group is selected from perfluorinated alkyl groups.

29. For formula (A), R ９ and R １０ each independently represents a linear or branched chain C １ ~C ５ 29. The electrochromic composition of claim 28, wherein the alkyl group is selected from perfluorinated alkyl groups.

30. For formula (A), R ９ and R １０ 30. The electrochromic composition of claim 29, wherein each is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

31. The anode component is represented by the following formula (I) or formula (II): 【Chemistry 8】 (For formula (I), R １ is selected from divalent linear or branched alkane linking groups; For formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

28. The electrochromic composition of claim 27, comprising at least one anodic component anion selected from the group consisting of:

32. (i) a cathodic component having a cathodic charge, the cathodic component further comprising a counter anion, each counter anion of the cathodic component being an anodic component having an anion covalently bound thereto; (ii) an optional electrolyte; and (iii) a polymeric thickener comprising a polymer, the polymer being poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 9】 (In the formula, R ９ and R １０ are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl. and a polymeric thickener, the anion of which is represented by (iv) a solvent; 1. An electrochromic composition comprising:

33. For formula (A), R ９ and R １０ each independently represents fluorine, linear or branched C １ ~C １０ Fluorinated alkyl or linear or branched C １ ~C １０ 33. The electrochromic composition of claim 32, wherein the alkyl group is selected from perfluorinated alkyl groups.

34. For formula (A), R ９ and R １０ each independently represents a linear or branched chain C １ ~C ５ 34. The electrochromic composition of claim 33, wherein the alkyl group is selected from perfluorinated alkyl groups.

35. For formula (A), R ９ and R １０ 35. The electrochromic composition of claim 34, wherein each is trifluoromethyl and the polymer of the polymer matrix comprises poly((diallyldimethylammonium)bis(trifluoromethane)sulfonimide).

36. 33. The electrochromic composition of claim 32, wherein the cathodic component having a cationic charge and the anodic component to which the anion is covalently bonded have a combined net neutral charge.

37. The anodic component having a covalently bound anion is represented by the following formula (I) or (II): 【Chemistry 10】 (For formula (I), R １ is selected from divalent linear or branched alkane linking groups; For formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

33. The electrochromic composition of claim 32, wherein the anodic component is selected from the anodic components represented by at least one of:

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