Electrochromic Devices and Compositions Including Cathodic Zwitterions

Abstract

The present invention relates to electrochromic devices and compositions that include a cathode component that includes a cathodic zwitterion, where an anion is covalently attached to a pyridinium nitrogen of the cathode component by a divalent linking group. Each covalently attached anion can independently be represented by the following formula (III) or formula (IV): It is expressed as: [Formula 1] JPEG2025514076000045.jpg31156 With reference to formula (III) and formula (IV), R 6 and R 7 is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R 8 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

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 / 333,234, filed April 21, 2022, and U.S. Nonprovisional Patent Application No. 18 / 130,932, filed April 5, 2023, the disclosures of which, in each case, are incorporated herein by reference in their entireties.

[0002] The present invention relates to electrochromic devices and compositions that include a cathode component that includes a cathodic zwitterion, where an anion is covalently bonded to a pyridinium nitrogen of the cathode component by a divalent linking group. [Background technology]

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

[0004] Electrochromic devices typically include opposing electrodes (e.g., an anode and a cathode) with a solution or gel-based electrochromic layer between them. The kinetics of such electrochromic devices are typically governed primarily by mass transport of cathodic and anodic components across the electrochromic layer. In some electrochromic systems, the cathodic components are positively charged and the anodic components are neutral or uncharged. In such systems, the positively charged cathodic components are typically transported across the electrochromic layer toward the cathode at a higher rate than the uncharged anodic components that diffuse toward the anode. Such transport imbalance can result in undesirable overpotential buildup at the anode interface and corresponding overoxidation. Overoxidation can undesirably result in reduced durability of the electrochromic device.

[0005] It would be desirable to develop new electrochromic devices and compositions whose active components, particularly the cathodic and anodic components, provide improved mass transport balance. It would further be desirable for such newly developed electrochromic devices and compositions to provide or be otherwise associated with improved durability, reduced manufacturing and / or operating costs, and / or improved operational efficiency. Summary of the Invention

[0006] According to the present invention, there is provided an electrochromic device comprising: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer, the first transparent electrode layer and the second transparent electrode layer being spaced apart in opposing positions; 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. The cathode component comprises a cathode component having a cationic charge selected from at least one of 1,1'-disubstituted-4,4'-dipyridinium cations represented by the following formula (I) or 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cations represented by the following formula (II). [ka]

[0007] With reference to formula (I) and formula (II), R 1 , R 2 , R 3 and R 5 is, independently at each occurrence, linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, substituted aryl, The following formula (III): [ka] and The following formula (IV): [ka] The group represented by the formula:

[0008] With reference to formula (III) and formula (IV), R 6 and R 7is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R 8 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. With further reference to formula (II), R 4 is selected from divalent linear or branched alkane linking groups. 1 and R 2 is provided that at least one of R is independently selected from a group represented by formula (III) or a group represented by formula (IV). 3 and R 5 is independently selected from a group represented by formula (III) or a group represented by formula (IV).

[0009] According to the present invention, there is further provided an electrochromic composition comprising (i) a cathode component, (ii) an anode component, (iii) an optional electrolyte, (iv) a polymeric thickener, and (v) a solvent. The cathode component of the electrochromic composition comprises a cathode component having a cationic charge selected from at least one of 1,1'-disubstituted-4,4'-dipyridinium cation represented by formula (I) as provided above or 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by formula (II) as provided above. For formulas (I) and (II), R 1 , R 2 , R 3 and R 5 is independently selected at each occurrence from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, substituted aryl, a group represented by formula (III) as provided above, and a group represented by formula (IV) as provided above. For formulas (III) and (IV), R 6 and R 7 is independently selected at each occurrence from a divalent linear or branched alkane linking group. 8is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. 4 is selected from divalent linear or branched alkane linking groups. 1 and R 2 is provided that at least one of R is independently selected from a group represented by formula (III) or a group represented by formula (IV). 3 and R 5 is independently selected from a group represented by formula (III) or a group represented by formula (IV).

[0010] The features which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. These and other features of the invention, its operating advantages, and certain 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]

[0011] [Figure 1] 1 is a representative cross-sectional side elevation view of an electrochromic device according to the present invention.

[0012] [Diagram 2] 1 is a graphical representation of a plot of % transmission versus wavelength obtained from an electrochromic device according to the present invention in an activated (dark) and non-activated (light) state, as described in the Examples herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In Figures 1 and 2, like characters sometimes refer to the same components and / or elements unless otherwise stated.

[0014] As used herein, the articles "a," "an," and "the" include plural referents unless specifically and explicitly limited to one referent.

[0015] Unless otherwise stated, all ranges or ratios disclosed herein should be understood to encompass any and all values ​​and subranges or subratios subsumed therein. For example, a range or ratio described as "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) the minimum value of 1 and the maximum value of 10, i.e., without limitation, 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 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0016] 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 its right-to-left representation [ka] or equivalently, -O(O)C- or -OC(O)-.

[0017] Except in the operating examples, or unless otherwise expressly stated, 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."

[0018] 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.

[0019] 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).

[0020] As used herein, the term "polymer" refers to homopolymers (eg, prepared from a single monomeric type), copolymers (eg, prepared from at least two monomeric types), and graft polymers.

[0021] 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.

[0022] 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.

[0023] As used herein, the term "electric potential" and related terms such as "electrical potential" refer to an electrical potential that can induce 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.

[0024] 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 purposes of non-limiting illustration, the first and second states of an electrochromic compound, such as anodically colored electrochromic compound, may differ with respect to at least one optical property, such as, but not limited to, the absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, an anodically colored electrochromic compound of the present invention may have different absorption spectra in each of the first and second states. For example, but not limited to, herein, an anodically colored electrochromic compound may be transparent in the first state and colored in the second state. Alternatively, an anodically colored electrochromic compound may have a first color in the first state and a second color in the second state.

[0025] As used herein, the term "display" means a visible or machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors, and security elements such as security marks.

[0026] As used herein, the term "window" means an opening adapted to permit the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and optical switches.

[0027] As used herein, the term "mirror" means a surface that specularly reflects a large portion of incident light.

[0028] As used herein, spatial or directional terms such as "left," "right," "inside," "outside," "upper," "lower," and the like, refer to the present invention as shown 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.

[0029] 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.

[0030] As used herein, the terms "intervening" and "intervening between" mean present or disposed between, but not necessarily in direct (or abutting) contact with, an overlying and / or underlying element or surface 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.

[0031] All documents, including but not limited to issued patents and patent applications, referenced herein are to be deemed "incorporated by reference" in their entirety, unless otherwise noted.

[0032] As used herein, the recitation of "straight chain or branched" groups, such as straight chain or branched alkyl, is defined herein as follows: methylene or methyl groups; linear groups, e.g., linear C-C alkyl groups; 20 Alkyl groups; and appropriately branched groups, such as branched C-C 20 It is understood to include alkyl groups.

[0033] As used herein, the term "alkyl" refers to a linear or branched, cyclic or non-cyclic C1-C 25 The straight or branched alkyl group is C1 to C 25 Alkyl, e.g. C1-C 20 Alkyl, e.g. C2-C 10 Alkyl, e.g. C1-C 12 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 suitably cyclic group, such as, but not limited to, a C3-C6 alkyl group. 12 Cycloalkyl (including but not limited to cyclic C3-C 10 "cycloalkyl" refers to a cycloalkyl group, including a cyclic C5-C7 alkyl group. 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.

[0034] As used herein, the term "heterocycloalkyl" refers to a suitably cyclic group, such as, but not limited to, C2-C 12 Heterocycloalkyl groups, such as C2-C 10Heterocycloalkyl groups, such as C5-C7 heterocycloalkyl groups, have at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. 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.

[0035] 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.

[0036] 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 pi electrons) significantly greater than the stability of a hypothetical localized structure. Examples of aryl groups include C6-C 14 Aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl.

[0037] The term "heteroaryl" as used herein includes, but is not limited to, C-C 18 Heteroaryl, for example, but not limited to, C-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.

[0038] 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.

[0039] The term "nitrogen-containing heterocycle", e.g., "nitrogen-containing heterocyclic group" or nitrogen-containing heterocyclic substituent", as used herein, includes, but is not limited to, nitrogen-containing rings to which the nitrogen-containing ring is attached via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amino (or alicyclic amino), such as morpholino, piperidino, pyrrolidino, and decahydroisoquinolino; and heteroaromatics, such as imidazole, pyrrole, indole, and carbazole.

[0040] 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, hydroxyl substituted aryls such as phenols, poly-fused ring aryls); aralkyl groups; heteroaryl groups (including poly-fused ring heteroaryl groups); amino groups, such as -N(R 11’ )(R 12’ ), where 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, classes and examples as further described herein, etc. According to some embodiments of the present invention, the substituents of the substituted groups are more specifically recited.

[0041] 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, such as -F, -Cl, -Br, and -I.

[0042] 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 in which at least one and up to all of its available hydrogen radicals are replaced with a halo group, such as, 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 in which all of its available hydrogen radicals are replaced with a halo group. For non-limiting illustrative purposes, perhalomethyl is -CX3 and perhalophenyl is -CX5, where X represents one or more halo groups, such as, but not limited to, F, Cl, Br, or I.

[0043] 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" refer to any one of A, B, or C, or any combination of 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.

[0044] As used herein, "selected from" is synonymous with "chosen from," regardless of whether the elements are listed conjunctively or disjunctively. Additionally, the phrases "selected from A, B, and C" and "selected from A, B, or C" refer to any one of A, B, or C, respectively, or any combination of 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.

[0045] The description of the invention herein may describe certain features as "particularly" or "preferred" within certain limitations (e.g., "preferred," "more preferred," or "even more preferred" within certain limitations). It is to be understood that the invention is not limited to or by such specific or preferred limitations, but rather encompasses the full scope of the present disclosure.

[0046] 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 other than hydrogen.

[0047] 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.

[0048] 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", means a carboxylic acid ester group represented by -C(O)OR, where R is selected from the groups described below other than hydrogen.

[0049] 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, include materials represented by -OC(O)R, where R is selected from the groups described below.

[0050] 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.

[0051] 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, other than hydrogen.

[0052] As used herein, and according to some embodiments, the term "carbamate" in reference to groups and substituents of various groups of compounds and components of the invention, and related terms such as "carbamate group" and "carbamate substituent" include 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.

[0053] 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, include materials represented by -N(R)C(O)N(R)(R), where each R is independently selected from the groups described below.

[0054] 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 invention, and related terms such as "siloxy group" and "siloxy substituent" include materials represented by -O-Si(R)3, where each R is independently selected from the groups described below, other than hydrogen.

[0055] As used herein, and according to some embodiments, the term "alkoxysilane" with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms such as "alkoxysilane group" and alkoxysilane substituents, 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 groups described below other than hydrogen.

[0056] 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 the following formula (B): [ka] This includes materials represented by the formula:

[0057] With reference to formula (A), t' is 2 or more, for example, 2 to 200, and R f and R g are each independently selected from the group R described below other than hydrogen; R h are independently a group R described below.

[0058] Unless otherwise specified, each R group of each of the above ketone, ester (carboxylic acid ester), carboxylate, amide, carbonate, carbamate, urea, siloxane, alkoxysilane, and polysiloxane groups is independently selected in each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including the classes and examples thereof listed herein above.

[0059] According to the present invention, the electrochromic material (of the electrochromic layer of the electrochromic device) comprises a cathode material having a cationic charge selected from at least one of 1,1'-disubstituted-4,4'-dipyridinium cations represented by formula (I) as previously described herein, and / or 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cations represented by formula (II) as previously described herein.

[0060] R in formula (I) 1 and R 2 and R of formula (II) 3and R 5 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. 1 and R 2 and R of formula (II) 3 and R 5 The cycloalkyl groups of the unsubstituted and substituted cycloalkyl groups, each of which may be independently selected, include those cycloalkyl groups listed herein above, such as, but not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0061] R in formula (I) 1 and R 2 and R of formula (II) 3 and R 5 Substituents for the substituted cycloalkyl and aryl groups, each of which may be independently selected, include those listed herein above. In some embodiments, R 1 and R 2 and R of formula (II) 3 and R 5 Each of the substituents of the substituted cycloalkyl and aryl groups, each of which may be independently selected, can each be 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.

[0062] R in formula (I) 1 and R 2 and R of formula (II) 3 and R 5Straight-chain or branched 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 propyl, straight-chain or branched butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, and straight-chain or branched heptyl.

[0063] According to some embodiments, and with reference to formula (I) and formula (II), R 1 , R 2 , R 3 and R 5 is, in each case independently, linear or branched C1-C 10 alkyl (or linear or branched C1-C8 alkyl, or linear or branched C1-C4 alkyl), unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl, substituted phenyl, anionic group represented by formula (III), and anionic group represented by formula (IV). With reference to formula (III) and formula (IV), according to some embodiments, R 6 and R 7 is, in each occurrence independently, a divalent linear or branched C 10 alkane linking group (or a divalent linear or branched C1-C8 alkane linking group, or a divalent linear or branched C1-C4 alkane linking group). With reference to Formula (IV), in some embodiments, R 8 Fluorine, linear or branched fluorinated C1-C 10 Alkyl (or linear or branched fluorinated C1-C8 alkyl, or linear or branched fluorinated C1-C4 alkyl), or linear or branched perfluorinated C1-C 10 alkyl (or linear or branched perfluorinated C1-C8 alkyl, or linear or branched perfluorinated C1-C4 alkyl). According to some embodiments, and with reference to formula (II), R 4 is a divalent linear or branched C1-C 10 alkane linking groups (or divalent linear or branched C1-C8 alkane linking groups, or divalent linear or branched C1-C4 alkane linking groups).

[0064] R in formula (IV) 8 With reference to, the term "linear or branched fluorinated alkyl" means an alkyl group in which at least one, and less than all, available hydrogens have been replaced with a fluoro group (F).

[0065] R in formula (II) 4 , R of formula (III) 6 and R of formula (IV) 7 Non-limiting examples of linear or branched divalent alkane groups from which each may be independently selected include divalent ethane, divalent linear or branched propane, divalent linear or branched butane, divalent linear or branched pentane, and divalent linear or branched hexane.

[0066] According to some embodiments of the present invention, and with reference to Formula (I) and Formula (II), R 1 , R 2 , R 3 and R 5 is independently selected in each occurrence from an anionic group represented by formula (III) or an anionic group represented by formula (IV).

[0067] For non-limiting illustrative purposes, R 1 and R 2 The cationic charge-bearing cathode component according to the present invention, as represented by formula (I), in which each of the groups represented by formula (III) is selected, can be prepared by N-alkylation of one mole of 4,4'-bipyridine with two moles of cyclic sulfonic acid ester, such as, but not limited to, 1,3-propane sultone and / or 1,4-butane sultone. A more detailed description of the relevant synthetic procedures is provided further herein in the examples.

[0068] For non-limiting illustrative purposes, R 1 Only R is selected from the group represented by formula (III); 2The cationic charged cathode component according to the present invention, as represented by formula (I), in which N is selected from linear or branched alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, can be prepared by N-alkylation of 1 mole of N-substituted 4,4'-bipyridinium monosalt with 1 mole of cyclic sulfonic acid ester, such as, but not limited to, 1,3-propane sultone and / or 1,4-butane sultone. The N-substituent of the N-substituted 4,4'-bipyridinium monosalt is selected from linear or branched alkyl, optionally substituted cycloalkyl, or optionally substituted aryl.

[0069] By way of further non-limiting example, R 1 and R 2 A cationic charged cathode component according to the present invention, as represented by formula (I), wherein each is selected from the group represented by formula (IV), can be prepared by reacting 1 mole of 4,4'-bipyridine with 2 moles of a ((chloroalkyl)sulfonyl)((fluoroalkyl or perfluoroalkyl)sulfonyl)amide salt.

[0070] By way of further non-limiting example, R 1 Only R is selected from the group represented by formula (IV); 2 A cationic charged cathode component according to the present invention, as represented by formula (I), in which is selected from linear or branched alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, can be prepared by reacting one mole of an N-substituted 4,4'-bipyridinium monosalt with one mole of a ((chloroalkyl)sulfonyl)((fluoroalkyl or perfluoroalkyl)sulfonyl)amide salt. The N-substituent of the N-substituted 4,4'-bipyridinium monosalt is selected from linear or branched alkyl, optionally substituted cycloalkyl, or optionally substituted aryl.

[0071] According to some embodiments of the present invention, the anode component is represented by the following formula (V) or formula (VI): [ka] The anode component anion includes at least one anode component anion selected from the group consisting of

[0072] Referring to formula (V), R 9 is selected from divalent linear or branched alkane linking groups. 10 is selected from divalent linear or branched alkane linking groups; R 11 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

[0073] The anodic component anion can be described as comprising an anodic moiety (group or site), such as a (10H-phenothiazin-10-yl) moiety, and an anion, such as a sulfonate anion or a triflamide anion, covalently bonded to the anodic moiety. In some further embodiments, the anion of the anodic component anion is covalently bonded to the anodic group or site by a divalent linear or branched alkane linking group. In some further embodiments, the anodic component anion is an anodic coloring electrochromic compound or group having an anion covalently bonded thereto.

[0074] R in formula (VI) 11 With reference to, the term "linear or branched fluorinated alkyl" means an alkyl group in which at least one, and less than all, available hydrogens have been replaced with a fluoro group (F).

[0075] With further reference to formula (V), according to some embodiments, R 9 is a divalent linear or branched C1-C 10 alkane linking group (or a divalent linear or branched C1-C8 alkane linking group, or a divalent linear or branched C1-C5 alkane linking group). With further reference to Formula (VI), in some embodiments, R 10 is a divalent linear or branched C1-C10 alkane linking group (or a divalent linear or branched C1-C8 alkane linking group, or a divalent linear or branched C1-C5 alkane linking group), R 11 Fluorine, linear or branched fluorinated C1-C 10 Alkyl (or linear or branched fluorinated C1-C8 alkyl, or linear or branched fluorinated C1-C5 alkyl), or linear or branched perfluorinated C1-C 10 alkyl (or linear or branched perfluorinated C1-C8 alkyl, or linear or branched perfluorinated C1-C5 alkyl).

[0076] In some non-limiting embodiments, R of formula (V) 9 and R of formula (VI) 10 are each independently selected from divalent methane, divalent ethane, divalent linear or branched propane, divalent linear or branched butane, and divalent linear or branched pentane. In some further non-limiting embodiments, R 11 is selected from fluorinated or perfluorinated versions or derivatives of methyl, ethyl, straight-chained or branched propyl, straight-chained or branched butyl, and straight-chained or branched pentyl.

[0077] According to some embodiments, a cathode component having a cationic charge and an anode component anion selected from at least one anode component anion represented by Formula (V) or Formula (VI) below, together have a net neutral charge.

[0078] In some embodiments, references herein to a counterion (such as a countercation and / or a counteranion) of a component refer 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.

[0079] By way of non-limiting example, according to some embodiments, R 1 Only R is selected from the group represented by formula (III);2 is selected from linear or branched alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, and the anodic component anion, which together have a net neutral charge, are represented by the following formula (VII): Formula (VII) [ka] It can be expressed as:

[0080] With reference to formula (VII), AA - is an anode component anion represented by formula (V) or formula (VI) described herein above. With further reference to formula (VII), R 6 is as described hereinbefore with reference to formula (III), and R 2 is selected from linear or branched alkyl, optionally substituted cycloalkyl, and optionally substituted aryl.

[0081] By way of non-limiting example, according to some embodiments, R 3 and R 5 are each independently selected from the group represented by formula (III) and the anodic component anion have a net neutral charge together and are represented by the following formula (VIII): Formula (VIII) [ka] It can be expressed as:

[0082] With reference to formula (VIII), each AA - is independently an anodic component anion represented by formula (V) or formula (VI) described hereinabove. With further reference to formula (VIII), each R 6 are independently as described hereinabove with reference to formula (III), and R 4is a divalent linking group as described hereinabove with reference to formula (II).

[0083] According to some further embodiments, the anode component comprising the anode component anion further comprises a counter cation. Classes and examples of cations from which each counter cation may be independently selected include, but are not limited to, alkali metal cations, such as lithium cations (Li + ), sodium 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-substituents and N,N-disubstituents 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.

[0084] 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 (C): Formula (C) [ka] The ammonium cation is selected from tetrasubstituted ammonium cations represented by the formula:

[0085] Referring to formula (C), 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 (B), R a , R b , R c and R d are each independently linear or branched C1 to C 10 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, linear or branched alkyl groups, cycloalkyl groups, and aryl groups.

[0086] In some embodiments, with reference to Formula (B), R a , R b , R c and R d In some further embodiments, each of R in formula (B) is independently selected from linear or branched alkyl. a , R b , R c and R d Each of the linear or branched C1 to C 10 alkyl (or straight chain or branched C1-C8 alkyl, or straight chain or branched C1-C5 alkyl).

[0087] In some embodiments, each countercation of the anode components is independently selected from tetra(linear or branched alkyl)ammonium cations. In some further embodiments, each countercation of the anode components is independently selected from tetra(linear or branched C1-C 10alkyl) ammonium cations.

[0088] In some embodiments, the anode component is composed of or otherwise consists of anode component anions selected from at least one anode component anion represented by Formula (V) or Formula (VI) and countercations, where the anode component has an equal number of anions and countercations and a corresponding neutral charge.

[0089] According to some embodiments, in addition to or instead of the anodic component anion having a covalently bound anion, for example represented by Formula (V) and / or Formula (VI), the anodic component of the electrochromic layer may contain one or more additional anodic electrochromic compounds, such as, but not limited to, ferrocene and / or ferrocene derivatives, at least one of which is substituted with at least one substituent, including those listed herein above; 5,10-dihydro-5,10-di(linear or branched C1-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 having a covalently bound anion), an additional cathodic component (or an additional suitable amount of a cathodic component) may also be present. In some embodiments, the additional cathodic component is represented by formula (I) and / or (II), but R 1 , R 2 , R 3 and R 5 in each case comprising one or more cathode components selected from formulas (III) and (IV).

[0090] According to some embodiments of the present invention, the cathode component further comprises a counter anion. In some further embodiments, the cathode component comprises an equal number of cations and counter anions (or anions), such that the cathode component has a corresponding net neutral charge. In some embodiments, each counter anion of the cathode component is BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , or B(phenyl)4 - In some embodiments, the counter anion of the cathodic component does not include or is not selected from the anodic component anions as represented by formulas (V) and (VI).

[0091] 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% to 6.25% by weight, or 0.5% to 5% by weight, or 1% to 3% by weight, the weight percentage in each case being based on the total weight of the electrochromic layer.

[0092] In some embodiments, the anodic component, such as but not limited to an anodic component having a covalently bound anion, 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 weight percentage in each case is based on the total weight of the electrochromic layer.

[0093] In some embodiments of the present invention, the electrochromic layer of the electrochromic device of the present invention comprises an electrolyte. In some embodiments, the electrolyte comprises at least one electrolyte anion and at least one electrolyte cation. In some embodiments, the electrolyte of the electrochromic layer comprises an equal number of electrolyte anions and electrolyte cations and has a corresponding net neutral charge.

[0094] In some embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion being independently selected from chloride, hexafluorophosphate, and bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide. 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(linear or branched C1-C6 alkyl)ammonium and tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl). 1-(linear or branched C1-C6 alkyl)ammonium; 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium; 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)pyrrolidinium; 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium; or a phosphonium cation, such as, but not limited to, tetra(linear or branched C1-C6 alkyl)phosphonium or tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl)phosphonium.

[0095] In some embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imides, and at least one electrolyte cation, each electrolyte cation independently selected from 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium, 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)pyrrolidinium, or 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium.

[0096] In some further embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion being a bis(trifluoromethylsulfonyl)imide, and at least one electrolyte cation, each electrolyte cation being independently selected from 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-1-butylpyrrolidinium, and 1-methyl-1-propylpiperidinium.

[0097] In some embodiments, the electrolyte is present in the electrochromic layer in an amount between 1% and 75% by weight, or between 5% and 50% by weight, or between 10% and 30% by weight, the weight percentage in each case being based on the total weight of the electrochromic layer.

[0098] According to some further embodiments, the electrochromic layer of the present invention includes a solvent. In some further embodiments, the solvent is present in the electrochromic layer instead of or in addition to the electrolyte. The solvent can include at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitriles, or di(linear or branched C1-C8) acetamides in some embodiments. 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 (or plasticizes) within the electrochromic layer. In some embodiments, the solvent is present in the electrochromic layer in an amount of 10% to 75% by weight or 20% to 60% by weight, the weight percentage in each case being based on the total weight of the electrochromic layer and the solvent.

[0099] The electrochromic layer of the electrochromic device of the present invention comprises a polymer matrix. The polymer matrix comprises at least one polymer. The polymer matrix, in some embodiments, is a gelled polymer matrix, a crosslinked polymer matrix, and / or a thermoplastic polymer matrix.

[0100] In some embodiments, the polymer matrix comprises a polymer, the polymer being poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)), poly(linear or branched C1-C8 alkyl)(meth)acrylate), or poly(diallyldimethylammonium X - ), and each X - are independently represented by the following formula (A): [ka] It is an anion represented by the formula:

[0101] Referring to formula (A), R 12 and R 13 are each independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

[0102] With reference to formula (A), the term "linear or branched fluorinated alkyl" means an alkyl group in which at least one, and less than all, available hydrogens have been replaced with a fluoro group (F).

[0103] In some embodiments, R of formula (A) 12 and R 13 are each independently fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0104] In some further embodiments, R of formula (A) 12 and R 13 are each independently selected from linear or branched C1-C5 perfluorinated alkyl.

[0105] In some further embodiments, R of formula (A) 12 and R 13 are each trifluoromethyl, and the polymer of the polymer matrix comprises poly((diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide), also referred to herein as poly((diallyldimethylammonium) bis(trifluoromethane)sulfonimide.

[0106] Poly(diallyldimethylammonium x) in the polymer matrix of the electrochromic layer - The substituted sulfonyl moiety of each of the substituted sulfonyl moieties of the poly(diallyldimethylammonium bis(substituted sulfonyl)imide anion) may be referred to herein as a poly((diallyldimethylammonium bis(substituted sulfonyl)imide anion)), R 12 and R 13 are independently selected from

[0107] In some embodiments, the polymer matrix poly(diallyldimethylammonium x - ) polymer has the following formula (D): [ka] It can be described with reference to:

[0108] Referring to formula (D), each X - are independently anions of formula (A) as previously described herein. In light of the difficulty in determining the Mn of poly(diallyldimethylammonium) polymers such as those of formula (D), and not intending to be bound by any theory, n in formula (D) 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.

[0109] In some embodiments of the present invention, poly(diallyldimethylammonium x - ) The polymer has a Mw of less than 100 kDa, or between 200 and 350 kDa, or between 400 and 500 kDa.

[0110] In some embodiments, poly(diallyldimethylammonium X - ) Polymers can be prepared according to the non-limiting synthetic descriptions provided in the examples further herein.

[0111] According to some embodiments of the present invention, the polymer matrix of the electrochromic layer comprises a polymer, the polymer being poly(diallyldimethylammonium x - ), each X - are independently anions represented by formula (A) as described above.

[0112] In some embodiments, the polymer matrix 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, the weight percentage in each case being based on the total weight of the electrochromic layer.

[0113] The electrochromic layer of the electrochromic device of the present invention may further include one or more art-recognized optional additives, in some embodiments, including but not limited to thermal stabilizers, UV stabilizers, rheology modifiers, static colorants (such as static dyes and / or static pigments), kinetic additives (to promote electrode reactions), and combinations thereof. A non-limiting class of art-recognized thermal stabilizers is phenols, such as 2,6-ditertiarybutylphenol and compounds containing 2,6-ditertiarybutylphenol groups or moieties. 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 2,2,6,6-tetramethylpiperidine groups or moieties. Static colorants include colorants whose absorption spectrum does not change in response to actinic radiation (such as UV and / or visible light) or application of an electric potential, and do not include photochromic and electrochromic compounds. Non-limiting classes of kinetic additives include salts such as alkali and alkaline earth metal salts of perchlorates, tetrafluoroborates and hexafluorophosphates, as well 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, such as 0.05% to 5% by weight, based on the total solids weight (including the weight of the optional additive) of the electrochromic layer.

[0114] 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.

[0115] 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 conductive first transparent electrode layer (20). 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) is present in the form of one or more patterns (such as one or more designs and / or indicia) 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). In some embodiments, the first transparent electrode layer (20) is in electrical contact with at least one first conductor (21), which may be a first conductive wire.

[0116] The electrochromic device (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) comprises a conductive second transparent electrode layer (32). 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) is present in the form of one or more patterns (such as one or more designs and / or marks) 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). In some embodiments, the second transparent electrode layer (32) is in electrical contact with at least one second conductor (33), which may be a second conductive second wire.

[0117] With further reference to the electrochromic device (3) of FIG. 1, the first transparent electrode layer (20) and the second transparent electrode layer (32) are opposed in opposing positions relative to one another and in spaced apart relation.

[0118] The electrochromic device (3) further comprises an electrochromic layer (35) interposed between the first transparent electrode layer (20) and the second transparent electrode layer (32). In some embodiments, the electrochromic layer (35) is interposed between and in contact with the first transparent electrode layer (20) and the second transparent electrode layer (32).

[0119] The first and second substrates of the electrochromic device are, in some embodiments of the present invention, each independently selected from a transparent substrate. The transparent substrates from which the first and second substrates may 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 may be independently selected are made from materials including silica glass. The first and second substrates may, in some embodiments, each independently have any suitable thickness. In some embodiments, the first and second substrates may, in some embodiments, each independently have a thickness of 1 mm to 25 mm, or 2 mm to 10 mm.

[0120] 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 carbon 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, and 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 carbon 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 device is a reflective electrochromic device, such as a controllable reflective mirror.

[0121] According to some embodiments, the first and second electrode layers of the electrochromic devices 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.

[0122] The first and second electrode layers of an electrochromic device, according to some embodiments of the present invention, can each independently have any suitable thickness, provided that they are transparent and conductive. In some embodiments, the first and second electrode layers of an electrochromic device of the present invention each independently have a thickness of 0.01 micrometers to 10 micrometers.

[0123] Examples of articles, such as articles of manufacture, that may include or be defined by the electrochromic devices 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; any other article or application where variable and controllable light transmission and / or color is desired.

[0124] The present invention also relates to an electrochromic composition comprising (i) a cathode component, (ii) an anode component, (iii) an optional electrolyte, (iv) a polymeric thickener, and (v) a solvent. The cathode component of the electrochromic composition comprises at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by formula (I) as previously described herein, or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by formula (II) as previously described herein. As previously described herein, for formula (I), R 1 and R 2 is provided that at least one of R is independently selected from a group represented by formula (III) or a group represented by formula (IV). As further described herein above, for formula (II), R 3 and R 5 is provided that at least one of is independently selected from a group represented by formula (III) or a group represented by formula (IV).

[0125] The cathode component, the anode component, the anode component anion, the optional electrolyte, and the polymeric thickener of the electrochromic composition are each as previously described herein with respect to the electrochromic device of the present invention.

[0126] The electrochromic compositions of the present invention include a solvent. In some embodiments, the solvent of the electrochromic composition includes at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitriles, or di(linear or branched C1-C8) acetamide.

[0127] According to some embodiments, the anode component comprising the anode component anion further comprises a counter cation. The class and examples of cations from which each counter cation is derived may be independently selected from the classes and examples listed herein above with respect to electrochromic devices. In some embodiments of the electrochromic composition of the present invention, each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations. According to some further embodiments, each counter cation is independently selected from tetra(linear or branched C1-C 10 alkyl) ammonium cations.

[0128] In some embodiments, the cathode component of the electrochromic composition further comprises a counter anion, and each counter anion of the cathode component is BF4. - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - or B(phenyl)4 - In some embodiments, the counter anion of the cathodic component of the electrochromic composition does not include or is not selected from the anodic component anions as represented by formulas (V) and (VI).

[0129] The cathodic component having a cationic charge, in some embodiments, is present in the electrochromic composition in an amount of 0.25% to 6.25% by weight, or 0.5% to 5% by weight, or 1% to 3% by weight, the weight percentage in each case being based on the total weight of the electrochromic composition.

[0130] In some embodiments, the anodic component, such as, but not limited to, an anodic component having a covalently bound anion, 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 weight percentage in each case is based on the total weight of the electrochromic composition.

[0131] In some embodiments, 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 %, where the weight percentage in each case is based on the total weight of the electrochromic composition.

[0132] In some embodiments, the polymeric thickener is present in the electrochromic composition in an amount of 5% to 80% by weight, or 10% to 60% by weight, or 15% to 50% by weight, the percent weight in each case being based on the total weight of the electrochromic composition.

[0133] In some embodiments, the solvent is present in the electrochromic composition in an amount of 10-75% by weight, or 20-60% by weight, or 25%-50% by weight, the percent weight in each case being based on the total weight of the electrochromic composition.

[0134] The electrochromic compositions of the present invention may, in some embodiments, 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 dyes and / or static pigments), kinetic additives (to promote electrode reactions), and combinations thereof. The optional additives, in each case, are as described hereinabove with respect to the electrochromic devices of the present invention. Each optional additive may be present in the electrochromic composition in any suitable active amount (e.g., 0.05% to 5% by weight) based on the total weight of the electrochromic composition (including the weight of the optional additives).

[0135] According to some embodiments of the present invention, the electrochromic layer of an 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 polymeric thickener are mixed under shear (e.g., with an impeller) until a homogenous mixture is formed. Second, the polymeric thickener is added and the combination is subjected to homogenization, resulting in the formation of a thick slurry. Using a doctor blade or drawdown bar or the like, a liquid film of the thick slurry is formed on a sacrificial or temporary liner (composed of polyethylene terephthalate in some embodiments). The liquid film, while on the sacrificial / temporary liner, is subjected to an elevated temperature, such as 60°C to 90°C, for 3 to 10 minutes, resulting in the formation of a solidified film / layer, which is the electrochromic layer. The solidified film / electrochromic layer is separated from the sacrificial / temporary liner (which is discarded), cut to size (if necessary), and placed on or directly on the first transparent electrode layer of the first substrate. A second transparent electrode of the second substrate is placed on or directly on the other (or opposing / 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 may further include electrical connectors that separately electrically contact the first and second transparent electrodes. The stack (with an optional 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.

[0136] According to some further embodiments, the polymeric thickener of the electrochromic composition is poly(diallyldimethylammonium xanthate), as previously described herein. - ) or poly(diallyldimethylammonium X- ), the electrochromic layer may be prepared therefrom according to the following general description. First, all components of the electrochromic composition except the polymeric thickener are mixed under shear (e.g., with an impeller) until a homogenous mixture is formed. Second, the polymeric 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 onto 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 (if necessary), and placed on or directly on the first transparent electrode layer of the first substrate. A second transparent electrode of a second substrate is disposed on or directly on the other (or opposing / 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 an optional 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.

[0137] The present invention may be further characterized by one or more of the following non-limiting clauses.

[0138] Clause 1: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer; the first transparent electrode layer and the second transparent electrode layer are opposed to each other and spaced apart from each other; (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; and (iv) a polymer matrix; an electrochromic layer comprising: The cathode component comprises a cathode component having a cationic charge selected from at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (I) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (II): [ka] In the formula (I) and (II), R 1 , R 2 , R 3 and R 5 is independently, at each occurrence, a straight chain or branched alkyl, an unsubstituted cycloalkyl, a substituted cycloalkyl, an unsubstituted aryl, a substituted aryl, a group represented by the following formula (III): [ka] and The following formula (IV): [ka] is selected from the group represented by In the formula (III) and the formula (IV), R 6 and R 7 is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R 8is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; With respect to formula (II), R 4 is selected from divalent linear or branched alkane linking groups; However, in formula (I), R 1 and R 2 is independently selected from the group represented by formula (III) or the group represented by formula (IV), However, in formula (II), R 3 and R 5 At least one of is independently selected from the group represented by formula (III) or the group represented by formula (IV), Electrochromic device.

[0139] Clause 2: For formula (I) and formula (II), R 1 , R 2 , R 3 and R 5 In each case independently, linear or branched C1-C 10 selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl, substituted phenyl, the group represented by formula (III), and the group represented by formula (IV); In the formula (III) and the formula (IV), R 6 and R 7 is, independently in each occurrence, a divalent linear or branched C 10 alkane linking groups, and for formula (IV), R 8 Fluorine, linear or branched fluorinated C1-C 10 Alkyl, or linear or branched perfluorinated C1-C 10 alkyl, With respect to formula (II), R 4 Divalent linear or branched C1-C 10 alkane linking groups, 2. An electrochromic device as described in clause 1.

[0140] Clause 3: The anode component is represented by the following formula (V) or formula (VI): [ka] and at least one anode component anion selected from the group consisting of In the formula (V), R 9 is selected from divalent linear or branched alkane linking groups; For formula (VI), R 10 is selected from divalent linear or branched alkane linking groups; R 11 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; Electrochromic device according to clause 1 or 2.

[0141] Clause 4: For formula (V), R 9 Divalent linear or branched C1-C 10 alkane linking groups, For formula (VI), R 10 Divalent linear or branched C1-C 10 alkane linking groups; R 11 Fluorine, linear or branched fluorinated C1-C 10 Alkyl, or linear or branched perfluorinated C1-C 10 selected from alkyl, 4. An electrochromic device as described in clause 3.

[0142] Clause 5: The electrochromic device of clause 3 or 4, wherein the cathode component having a cationic charge and the anode component anion selected from at least one anode component anion represented by Formula (V) or Formula (VI) together have a net neutral charge.

[0143] Clause 6: The electrochromic device of clause 3 or 4, wherein the anode component further comprises a counter cation.

[0144] Clause 7: The electrochromic device of clause 6, 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.

[0145] Clause 8: Each counter cation has the following formula (C): Formula (C) [ka] and independently selected from tetra-substituted ammonium cations represented by 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; Electrochromic device according to clause 6 or 7.

[0146] Article 9:R a , R b , R c and R d are each independently linear or branched C1 to C 10 9. The electrochromic device of claim 8, wherein the alkyl group is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0147] Article 10:R a , R b , R c and R d are each independently linear or branched C1 to C 10 10. The electrochromic device of claim 8 or 9, wherein the alkyl is selected from the group consisting of aryl, ... and alkyl.

[0148] Clause 11: The electrochromic device of any one of clauses 6, 7, 8, 9 or 10, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0149] Clause 12: Each countercation is a tetra (linear or branched C1-C 10 12. The electrochromic device of any one of clauses 6, 7, 8, 9, 10 or 11, wherein the cations are independently selected from the group consisting of alkyl) ammonium cations.

[0150] Clause 13: The cathode component further comprises a counter anion, and each counter anion of the cathode component is BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , or B(phenyl)4 - 13. The electrochromic device of any one of clauses 1, 2, 3, 4, 6, 7, 8, 9, 10, 11 or 12, selected from the group consisting of:

[0151] Clause 14: The electrolyte is present, at least one electrolyte anion, each electrolyte anion being independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imides; at least one electrolyte cation, each electrolyte cation being independently selected from 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium, 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium, a phosphonium cation, such as, but not limited to, tetra(linear or branched C1-C6 alkyl)phosphonium, or tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl)phosphonium, or an ammonium cation, such as, but not limited to, tetra(linear or branched C1-C6 alkyl)ammonium, and tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl)ammonium; 14. The electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, comprising:

[0152] Clause 15: The polymer matrix comprises a polymer, and the polymer is selected from the group consisting of poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)), poly((linear or branched C1-C8 alkyl)(meth)acrylate) and poly(diallyldimethylammonium X - ), and each X - are independently represented by the following formula (A): [ka] is an anion represented by In the formula, R 12 and R 13 are each independently fluorine, linear or branched fluorinated alkyl (or linear or branched fluorinated C1-C 10 alkyl; or linear or branched fluorinated C1-C8 alkyl; or linear or branched fluorinated C1-C5 alkyl), or linear or branched perfluorinated alkyl (or linear or branched perfluorinated C1-C 10alkyl; or linear or branched perfluorinated C1-C8 alkyl; or linear or branched perfluorinated C1-C5 alkyl), 15. The electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0153] Clause 16. The polymer matrix comprises a polymer, the polymer being poly(diallyldimethylammonium x - ), each X - are independently represented by the following formula (A): [ka] is an anion represented by In the formula, R 12 and R 13 are each independently fluorine, linear or branched fluorinated alkyl (or linear or branched fluorinated C1-C 10 or linear or branched fluorinated C1-C8 alkyl; or linear or branched fluorinated C1-C5 alkyl), or linear or branched perfluorinated alkyl (or linear or branched perfluorinated C1-C 10 alkyl; or linear or branched perfluorinated C1-C8 alkyl; or linear or branched perfluorinated C1-C5 alkyl), 16. The electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15.

[0154] Clause 17: An article of manufacture comprising the electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, and selected from an energy efficient transparent film, a transparent film for privacy, a mirror, an optical filter or an ophthalmic article.

[0155] Article 18: (i) a cathode component; (ii) an anode component; (iii) an optional electrolyte; and (iv) a polymeric thickener; and (v) a solvent; Including, The cathode component comprises a cathode component having a cationic charge selected from at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (I) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (II): [ka] In the formula (I) and (II), R 1 , R 2 , R 3 and R 5 is, independently at each occurrence, linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, substituted aryl, The following formula (III): [ka] and a group represented by the following formula (IV): [ka] is selected from the group represented by In the formula (III) and the formula (IV), R 6 and R 7 is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R 8 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; With respect to formula (II), R 4 is selected from divalent linear or branched alkane linking groups; However, in formula (I), R 1 and R 2is independently selected from the group represented by formula (III) or the group represented by formula (IV), However, in formula (II), R 3 and R 5 At least one of is independently selected from the group represented by formula (III) or the group represented by formula (IV), Electrochromic compositions.

[0156] Clause 19: For formula (I) and formula (II), R 1 , R 2 , R 3 and R 5 In each case independently, linear or branched C1-C 10 selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl, and substituted phenyl, the group represented by formula (III), and the group represented by formula (IV); In the formula (III) and the formula (IV), R 6 and R 7 is, independently in each occurrence, a divalent linear or branched C 10 alkane linking groups, and for formula (IV), R 8 Fluorine, linear or branched fluorinated C1-C 10 Alkyl, or linear or branched perfluorinated C1-C 10 alkyl, With respect to formula (II), R 4 Divalent linear or branched C1-C 10 alkane linking groups, 19. The electrochromic composition of claim 18.

[0157] Clause 20: The anode component is represented by the following formula (V) or formula (VI): [ka] and at least one anode component anion selected from the group consisting of For formula (V), R 9 is selected from divalent linear or branched alkane linking groups; For formula (VI), R 10 is selected from divalent linear or branched alkane linking groups; R 11 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; 20. The electrochromic composition of claim 18 or 19.

[0158] Clause 21: For formula (V), R 9 Divalent linear or branched C1-C 10 alkane linking groups, For formula (VI), R 10 Divalent linear or branched C1-C 10 alkane linking groups; R 11 Fluorine, linear or branched fluorinated C1-C 10 Alkyl, or linear or branched perfluorinated C1-C 10 selected from alkyl, 21. The electrochromic composition of claim 20.

[0159] Clause 22: The electrochromic composition of clause 20 or 21, wherein the cathode component having a cationic charge and the anode component anion selected from at least one anode component anion represented by Formula (V) or Formula (VI), together have a net neutral charge.

[0160] Clause 23: The electrochromic composition of clause 20 or 21, wherein the anodic component further comprises a counter cation.

[0161] Clause 24: The electrochromic composition of clause 23, 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.

[0162] Clause 25: each counter cation is represented by the following formula (C): Formula (C) [ka] and independently selected from tetra-substituted ammonium cations represented by 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; 25. The electrochromic composition according to claim 23 or 24.

[0163] Article 26:R a , R b , R c and R d are each independently linear or branched C1 to C 10 26. The electrochromic composition of claim 25, wherein the alkyl is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0164] Article 27:R a , R b , R c and R d are each independently linear or branched C1 to C 10 27. The electrochromic composition of claim 25 or 26, wherein the alkyl is selected from the group consisting of aryl, ... and alkyl.

[0165] Clause 28: The electrochromic composition of any one of clauses 23, 24, 25, 26 or 27, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0166] Clause 29: Each counter cation is a tetra (linear or branched C1-C 1030. The electrochromic composition of any one of clauses 23, 24, 25, 26, 27 or 28, wherein the cation is independently selected from the group consisting of alkyl)ammonium cations.

[0167] Clause 30: The cathode component further comprises a counter anion, each counter anion of the cathode component being BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , or B(phenyl)4 - 30. The electrochromic composition of any one of clauses 18, 19, 20, 21, 23, 24, 25, 26, 27, 28 or 29, selected from the group consisting of:

[0168] Clause 31: The electrolyte is present, at least one electrolyte anion, each electrolyte anion being independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imides; at least one electrolyte cation, each electrolyte cation being independently selected from 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium or 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium; 31. The electrochromic composition of any one of clauses 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, comprising:

[0169] Clause 32: The polymer thickener comprises a polymer, the polymer being selected from the group consisting of poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)), poly((linear or branched C1-C8 alkyl)(meth)acrylate) and poly(diallyldimethylammonium X -), and each X - are independently represented by the following formula (A): [ka] is an anion represented by In the formula, R 12 and R 13 are each independently fluorine, linear or branched fluorinated alkyl (or linear or branched fluorinated C1-C 10 or linear or branched fluorinated C1-C8 alkyl; or linear or branched fluorinated C1-C5 alkyl), or linear or branched perfluorinated alkyl (or linear or branched perfluorinated C1-C 10 alkyl; or linear or branched perfluorinated C1-C8 alkyl; or linear or branched perfluorinated C1-C5 alkyl), 32. The electrochromic composition of any one of clauses 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or 31.

[0170] Clause 33. The polymer thickener comprises a polymer, the polymer being poly(diallyldimethylammonium x - ), each X - are independently represented by the following formula (A): [ka] is an anion represented by In the formula, R 12 and R 13 are each independently fluorine, linear or branched fluorinated alkyl (or linear or branched fluorinated C1-C 10 or linear or branched fluorinated C1-C8 alkyl; or linear or branched fluorinated C1-C5 alkyl), or linear or branched perfluorinated alkyl (or linear or branched perfluorinated C1-C 10alkyl; or linear or branched perfluorinated C1-C8 alkyl; or linear or branched perfluorinated C1-C5 alkyl), 33. The electrochromic composition of any one of clauses 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32.

[0171] Clause 34: The electrochromic composition of any one of clauses 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32 or 33, wherein the solvent comprises at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid ester of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitrile, or di(linear or branched C1-C8) acetamide.

[0172] The present invention is more particularly described in the following examples, which are intended to be illustrative only, and numerous modifications and variations will be apparent to those skilled in the art.

[0173] example Part 1 of the examples describes the synthesis of an anode component with a covalently bound anion according to the invention. Part 2 describes the synthesis of a cathode component according to the invention. Part 3 describes the synthesis of poly(diallyldimethylammonium X) according to the invention. - Part 2 describes the preparation of electrochromic devices according to the invention. Part 3 describes the preparation of electrochromic devices according to the invention. Part 4 describes the evaluation of the electrochromic devices according to Part 3.

[0174] Part 1 Synthesis Example 1 Referring to Scheme (1) below, a non-limiting illustration of the preparation of an anode component having a covalently bound anion according to the present invention, represented by formula (V), is provided, where R 9 is a divalent n-propane linking group.

[0175] 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 while purging with nitrogen. To the reaction mixture was added 2.4 g of 60% NaH (60 mmol). The solution was observed to turn deep red in color 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.

[0176] The reaction was quenched by adding 100 ml of deionized (DI) water and the solvent was removed by applying a vacuum, after which an oily material remained in the flask. 50 ml of ethyl acetate was added to the oily material, 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. Scheme (1) [ka]

[0177] Part 1 Synthesis Example 2 Referring to Scheme (2) below, a non-limiting illustration of the preparation of an anode component having a covalently bound anion according to the present invention, represented by formula (VI), is provided, where R 10 is a divalent n-propane linking group, R 11 is trifluoromethyl.

[0178] (3) Sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was prepared according to Synthesis Example 1. 1 gram (0.0029 mol) of (3) Sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was finely ground in a mortar and pestle and then placed in a 100 ml round bottom flask equipped with a magnetic stir bar and a reflux condenser with N2 sweep / blanket. 20 ml of acetone and 40 mg of 18-crown-6 ether were added to the flask and the mixture was stirred vigorously for 15 minutes. The solution became cloudy, but it was observed that solid sodium salt (3) was present. (4) Cyanuric acid chloride (540 mg, 0.0029 mol, 1 equiv.) was added with vigorous stirring under N2. The mixture was refluxed in an oil bath (approximately 80° C.) for 24 hours. The color of the solution turned orange 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.

[0179] (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 source was attached to the condenser and Schlenk funnel and secured with plastic clips. The vessel was flushed for 15 s using a strong nitrogen flux, 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), 50 ml of dry MeCN was added under nitrogen flux 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 bulky 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)propane-1-triflamide in the form of brown needles. Scheme (2) [ka]

[0180] Part 2 Synthesis Example 3 Referring to Scheme (3) below, a non-limiting illustration of the preparation of a cathode component according to the present invention represented by formula (I) is provided, wherein R 1 and R 2 are represented by formula (III), and R 6 is -CH2CH2CH2- in each case.

[0181] In a suitably sized round bottom flask, 2 g of 4,4'-bipyridine (13) was dissolved in 50 ml of dry MeCN, followed by the addition of a solution of 3.28 g of 1,3-propane sultone (14) in MeCN. The contents of the flask were refluxed overnight and then cooled to ambient room temperature. The resulting precipitate was collected and washed twice with MeCN to give 4.96 g of 3,3'-([4,4'-bipyridinium]-1,1'-diyl)bis(propane-1-sulfonate) (15). Scheme (3) [ka]

[0182] Part 2 Synthesis Example 4 Referring to Scheme (4) below, a non-limiting illustration of the preparation of a cathode component according to the present invention represented by formula (I) is provided, wherein R 1 is N-triflylpropane-1-sulfonamide, R 2 is phenyl and the counter anion is bis(trifluoromethane)sulfonimide. 4,4'-bipyridine (13) (20.3 g) and 1-chloro-2,4-dinitrobenzene (20) (15.6 g) were added to an Erlenmeyer flask equipped with a magnetic stirrer. Acetone (100 ml) was then added and a reflux condenser was connected. The reaction mixture was refluxed under stirring for 24 h. After cooling to room temperature, the mixture was filtered and the greenish solid was washed three times with hexane. The resulting solid was air-dried to give 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride (22) in 57–67% yield (20.5–24.0 g).

[0183] In an Erlenmeyer flask equipped with a magnetic stirrer, 5 g of (22) and ethanol (100 ml) were added. Then, aniline (24) (3.5 ml) was added under stirring. A reflux condenser was connected and the reaction mixture was refluxed for 2 h. The mixture was cooled to room temperature and the solvent was removed on a rotary evaporator. Water (200 ml) was added to the residue and the mixture was stirred at room temperature for 30 min. The mixture was filtered and the solution was evaporated on a rotary evaporator to give a yellow solid. The solid was washed three times with acetone and dried in air to give 1-phenyl-4,4'-bipyridinium chloride (26) in 95-99% yield (3.6-3.7 g).

[0184] In an Erlenmeyer flask equipped with a magnetic stirrer, 1-phenyl-1-4,4-bipyridinium chloride (26) (1 g) and acetonitrile (80 ml) were added. Then, while stirring, a solution of potassium 3-chloro-N-triflylpropane-1-sulfonamide (28) (1 eq.) in acetonitrile (20 ml) was added to the mixture. A reflux condenser was connected and the solution was refluxed under stirring for 4 h. After cooling to room temperature, the mixture was filtered and the solid was washed twice with acetonitrile and then dried in air to give ((3-(1'-phenyl-[4,4'-bipyridine]-1,1'-diium-1-yl)propyl)sulfonyl)triflamide (30) in 79% yield (1.2 g).

[0185] To a glass beaker equipped with a magnetic stirrer was added 1 g of (30) along with water (50 ml). The mixture was stirred until the starting reactants were completely dissolved, then a solution of lithium bis(trifluoromethane)sulfonimide (32) (1.2 equiv.) in water (10 ml) was added dropwise with vigorous stirring at room temperature. The mixture was stirred for 30 min and then filtered. The white solid was washed five times with water and air-dried to give (34), herein referred to as PhVT, in 77% yield (1.2 g). Scheme (4) [ka]

[0186] Part 3 Referring to the following scheme (5), poly(diallyldimethylammonium X) according to the present invention can be prepared by the following method. - A non-limiting description of the preparation of a ) polymer is provided, in which, with reference to formula (A) provided herein above, R 12 and R 13 Each is trifluoromethyl.

[0187] 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, with a reported Mw of 400-500 kDa) was added dropwise over a 10 min period (310 mmol of chloride). The contents of the flask were stirred vigorously at 800 rpm for 18 h, followed by cooling to ambient room temperature, allowing a precipitate to form. The precipitate was collected by vacuum filtration and washed several times with deionized water.

[0188] 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, followed by cooling 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 approximately 88% yield. Scheme (5) [ka]

[0189] Part 4 An electrochromic device according to the present invention was prepared according to the following procedure: An initial solution was prepared with magnetic stirring of sulfolane (5 g); 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonimide (EMIM-TFSI) (1 g); potassium 3-(10H-phenothiazin-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonamide (PTTK) (100 mg); and PhVT (see (34) in Scheme 4) (100 mg). 5 g of poly((diallyldimethylammonium bis(trifluoromethane)sulfonimide)) (PDADMA-TFSI) was added to the initial solution, and the combination was then subjected to vigorous stirring with heat to form a thick solution. While hot, a volumetric aliquot of this solution was drop cast onto a fluorine-doped tin oxide (FTO) glass electrode (3 in. x 4 in., 7.62 cm x 10.16 cm) with copper tape wrapped around the edges covered with insulating polyimide. A prefabricated thermoplastic gasket, 0.5 in. (1.27 cm) wide and 400 microns thick, was added to surround the active area. A second fluorine-doped tin oxide (FTO) glass electrode was placed on top of the electrochromic layer. The stack was subjected to vacuum lamination 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.

[0190] Part 5 Plots of transmission % vs. wavelength (nm) for the electrochromic device of Part 4 are shown in Figure 2 of the drawings in the light / deactivated and dark / activated states (at room temperature in each case). With reference to Figure 2, an electrochromic device according to the present invention provides a significant and desirable level of dimming (i.e., reduction in visible light transmission) when activated compared to its light / deactivated state. In Figure 2, the electrochromic device of Part 4 is referred to as a "PTTK-PhVT device" with respect to the plots of the light and dark states, followed by the term "switching." With further reference to Figure 2, the plot of transmission % vs. wavelength for the light / deactivated state is labeled "PhVT light state" and the plot of transmission % vs. wavelength for the dark / activated state is labeled "PhVT dark state."

[0191] 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 including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer; the first transparent electrode layer and the second transparent electrode layer are opposed to each other and spaced apart from each other; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) a cathode component; and (ii) an anode component; and (iii) an optional electrolyte; and (iv) a polymer matrix; an electrochromic layer comprising: The cathode component comprises a cathode component having a cationic charge selected from at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (I) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (II): 【Chemistry 1】 In the formula (I) and (II), R １ , R ２ , R ３ and R ５ is independently, at each occurrence, a straight or branched alkyl, an unsubstituted cycloalkyl, a substituted cycloalkyl, an unsubstituted aryl, a substituted aryl, a group represented by the following formula (III): 【Chemistry 2】 and The following formula (IV): 【Chemistry 3】 is selected from the group represented by In the formula (III) and the formula (IV), R ６ and R ７ is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R ８ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; For formula (II), R ４ is selected from divalent linear or branched alkane linking groups; In the formula (I), R １ and R ２ is independently selected from the group represented by formula (III) or the group represented by formula (IV), In the formula (II), R ３ and R ５ is independently selected from the group represented by formula (III) or the group represented by formula (IV), Electrochromic device.

2. For formula (I) and formula (II), R １ , R ２ , R ３ and R ５ is, independently in each occurrence, a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted phenyl, substituted phenyl, the group represented by formula (III), and the group represented by formula (IV); In the formula (III) and the formula (IV), R ６ and R ７ is, independently in each occurrence, a divalent linear or branched C １ ~C １０ alkane linking groups, and for formula (IV), R ８ is fluorine, linear or branched fluorinated C １ ~C １０ Alkyl, or linear or branched perfluorinated C １ ~C １０ alkyl, For formula (II), R ４ is a divalent linear or branched C １ ~C １０ alkane linking groups selected from The electrochromic device of claim 1 .

3. The anode component has the following formula (V) or (VI): 【Chemistry 4】 and at least one anode component anion selected from the group consisting of For formula (V), R ９ is selected from divalent linear or branched alkane linking groups; For formula (VI), R １０ is selected from divalent linear or branched alkane linking groups; R １１ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; The electrochromic device of claim 1 .

4. For formula (V), R ９ is a divalent linear or branched C １ ~C １０ alkane linking groups, For formula (VI), R １０ is a divalent linear or branched C １ ~C １０ alkane linking groups; R １１ is fluorine, linear or branched fluorinated C １ ~C １０ Alkyl, or linear or branched perfluorinated C １ ~C １０ selected from alkyl, The electrochromic device of claim 3.

5. 4. The electrochromic device of claim 3, wherein the cathodic component having a cationic charge and the anodic component anion have together a net neutral charge.

6. The electrochromic device of claim 3 , wherein the anodic component further comprises a counter cation.

7. 7. The electrochromic device of claim 6, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

8. The cathode component further comprises a counter anion, each counter anion of the cathode 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 － 2. The electrochromic device of claim 1 , wherein the organic solvent is selected from the group consisting of:

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

10. The polymer matrix comprises a polymer, the 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), poly((linear or branched C １ ~C ８ (alkyl) (meth) acrylate) or poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 5】 is an anion represented by In the formula, R １２ and R １３ 10. The electrochromic device of claim 1, wherein each is independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

11. The polymer matrix comprises a polymer, the polymer being poly(diallyldimethylammonium x － ), each X － are independently represented by the following formula (A): 【Chemistry 6】 is an anion represented by In the formula, R １２ and R １３ 10. The electrochromic device of claim 1, wherein each is independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

12. (i) a cathode component; and (ii) an anode component; and (iii) an optional electrolyte; and (iv) a polymeric thickener; and (v) a solvent; Including, The cathode component comprises a cathode component having a cationic charge selected from at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (I) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (II): 【Chemistry 7】 In the formula (I) and (II), R １ , R ２ , R ３ and R ５ is, independently at each occurrence, linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, substituted aryl, The following formula (III): 【Chemistry 8】 and a group represented by the following formula (IV): 【Chemistry 9】 is selected from the group represented by In the formula (III) and the formula (IV), R ６ and R ７ is independently selected at each occurrence from a divalent linear or branched alkane linking group; for formula (IV), R ８ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; For formula (II), R ４ is selected from divalent linear or branched alkane linking groups; In the formula (I), R １ and R ２ is independently selected from the group represented by formula (III) or the group represented by formula (IV), In the formula (II), R ３ and R ５ is independently selected from the group represented by formula (III) or the group represented by formula (IV): Electrochromic compositions.

13. For formula (I) and formula (II), R １ , R ２ , R ３ and R ５ is, independently in each occurrence, a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ selected from cycloalkyl, unsubstituted phenyl, and substituted phenyl, the group represented by formula (III), and the group represented by formula (IV); In the formula (III) and the formula (IV), R ６ and R ７ is, independently in each occurrence, a divalent linear or branched C １ ~C １０ alkane linking groups, and for formula (IV), R ８ is fluorine, linear or branched fluorinated C １ ~C １０ Alkyl, or linear or branched perfluorinated C １ ~C １０ alkyl, For formula (II), R ４ is a divalent linear or branched C １ ~C １０ alkane linking groups selected from The electrochromic composition of claim 12.

14. The anode component has the following formula (V) or (VI): 【Chemistry 10】 and at least one anode component anion selected from the group consisting of For formula (V), R ９ is selected from divalent linear or branched alkane linking groups; For formula (VI), R １０ is selected from divalent linear or branched alkane linking groups; R １１ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; The electrochromic composition of claim 12.

15. For formula (V), R ９ is a divalent linear or branched C １ ~C １０ alkane linking groups, For formula (VI), R １０ is a divalent linear or branched C １ ~C １０ alkane linking groups; R １１ is fluorine, linear or branched fluorinated C １ ~C １０ Alkyl, or linear or branched perfluorinated C １ ~C １０ selected from alkyl, The electrochromic composition of claim 14.

16. 15. The electrochromic composition of claim 14, wherein the cathodic component having a cationic charge and the anodic component anion together have a net neutral charge.

17. The electrochromic composition of claim 14 , wherein the anodic component further comprises a counter cation.

18. 20. The electrochromic composition of claim 17, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

19. The cathode component further comprises a counter anion, each counter anion of the cathode 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 － 13. The electrochromic composition of claim 12, selected from the group consisting of:

20. The electrolyte is present, At least one electrolyte anion, each electrolyte anion being bis(perfluoro(linear or branched C １ ~C ６ at least one electrolyte anion independently selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation being 1-(linear or branched C １ ~C ６ Alkyl)-3-(linear or branched C １ ~C ６ alkyl)imidazolium, 1-(linear or branched C １ ~C ６ Alkyl)-1-(linear or branched C １ ~C ６ Alkyl) piperidinium, tetra(linear or branched C １ ~C ６ alkyl)phosphonium, tri(C ５ ~C ８ Cycloalkyl)-(linear or branched C １ ~C ６ Alkyl)phosphonium, 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 independently selected from the group consisting of ammonium, ammonium cations, The electrochromic composition of claim 12 comprising:

21. The polymeric thickener comprises a polymer, the 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), poly((linear or branched C １ ~C ８ (alkyl) (meth) acrylate) or poly(diallyldimethylammonium X － ), each X － are independently represented by the following formula (A): 【Chemistry 11】 is an anion represented by In the formula, R １２ and R １３ 13. The electrochromic composition of claim 12, wherein each is independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

22. The polymeric thickener comprises a polymer, the polymer being poly(diallyldimethylammonium x － ), each X － are independently represented by the following formula (A): 【Chemistry 12】 is an anion represented by In the formula, R １２ and R １３ 13. The electrochromic composition of claim 12, wherein each is independently selected from fluorine, a linear or branched fluorinated alkyl, or a linear or branched perfluorinated alkyl.

23. The solvent may be 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 13. The electrochromic composition of claim 12, comprising at least one of:

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