Electrochemical compounds for low-current electrochromic devices

Abstract

Anodic redox species comprising phenazine compounds substituted with at least one sterically hindered group and electrochromic devices using these chemical compounds are disclosed.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 311,694, filed on 18 February 2022 (which is incorporated herein by reference in its entirety for all purposes).

[0002] This technology generally relates to electrochromic devices. More specifically, it relates to redox compounds suitable for use in electrochromic devices that have persistent color memory and can provide current during clearing for a considerable period after charging. [Background technology]

[0003] Electrochromic devices have been well-known for many years. When a sufficient potential is applied to a pair of electrodes, the electrochromic medium placed between the electrodes is activated, and its color and / or light transmittance can change. Taking advantage of this, devices such as dimmable mirrors and windows are becoming increasingly popular in industries such as automotive and aerospace.

[0004] This disclosure deals with phenazine electrochromic materials having improved weather-resistant stability properties for use in electrochromic devices, particularly as anodic redox species attached to or limited to polymer matrix films. [Overview of the project]

[0005] In one embodiment, a compound represented by the following is provided: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9Each is independently H, F, Cl, Br, I, CF3, CN, OR 11 , SR 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups of may combine to form a monocyclic, polycyclic, or heterocyclic group, each R 11 is independently H or alkyl, R 5 and R 10 are independently (i) -L1-A-L2-OR 14 represented by, each L1 is independently a C1-C8 alkylene group, each L2 is independently a C1-C8 alkylene group, each R 14 is H or alkyl, A is an ammonium group represented by -N(R 15 )2 + -, each R 15 is alkyl or alkyl hydroxy, or (ii) -L3-OR 16 represented by, each L3 is independently a C1-C8 alkylene group, each R 16 is H or alkyl, R 2 , R 3 , R 7 , and R 8 at least one of is a sterically hindered group.

[0006] In some embodiments, the sterically hindered group is selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

[0007] In some embodiments, R1 , R 3 , R 4 , R 6 , R 8 , and R 9 Each of these is independently H. In some embodiments, R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 Each of these is independently H.

[0008] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of them is independently a C2-C8 alkyl group. In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of these is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of these is independently isopropyl, neopentyl, or tertiary butyl.

[0009] In some embodiments, R 2 and R 7 , or R 2 and R 8 Each of these is independently a C2-C8 alkyl group. In some embodiments, R 2 and R 7 , or R 2 and R 8 Each of these is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 2 and R 7 , or R 2 and R8 is independently isopropyl, neopentyl, or tertiary butyl, respectively.

[0010] In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently C2-C8 alkyl. In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently isopropyl, neopentyl, or tertiary butyl, respectively.

[0011] In some embodiments, at least one of R 2 , R 3 , R 7 , and R 8 is independently aryl. In some embodiments, at least one of R 2 , R 3 , R 7 , and R 8 is independently phenyl.

[0012] In some embodiments, R 2 and R 7 , or R 2 and R 8 are each independently aryl. In some embodiments, R 2 and R 7 are each independently phenyl.

[0013] In some embodiments, R 3 and R 8 , or R 3 and R 7Each is independently aryl. In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently phenyl.

[0014] In some embodiments, at least one of R 5 and R 10 is independently represented by -L1-A-L2-OR 14 , where each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group, each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group, each R 14 is H or alkyl, A is an ammonium group represented by -N(R 15 )2 + , and each R 15 is C1-C8 alkyl or C1-C8 alkyl hydroxyl.

[0015] In some embodiments, each L1 is independently a C2 or C4 alkylene group, each L2 is independently a C3 alkylene group, each R 14 is H, A is an ammonium group represented by -N(R 15 ​​​​​​​​​​​​​​​​​​​​​n is 1, 2, 3, 4, 5, 6, 7, or 8. x is 1, 2, 3, 4, 5, 6, 7, or 8. Each R 15 These are independently C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0017] In some embodiments, n is 2 or 4, x is 3, and each R 15 These are independently C1 alkyl or C2 alkylhydroxyl.

[0018] In some embodiments, R 5 and R 10 At least one of them independently -L3-OR 16 Represented by, Each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each R 16 is either H or alkyl.

[0019] In some embodiments, each L3 is independently a C4 or C6 alkylene group, and each R 16 H is H.

[0020] In some embodiments, R 5 and R 10 At least one of these is independently represented as follows: [ka] y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0021] In some embodiments, y is 3 or 6.

[0022] In some embodiments, the compound is F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6- ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , BAr4 - or an ammonium salt having an anion comprising a mixture of the anion thereof, where Ar is an aryl group or a fluorinated aryl group. In some embodiments, the anion is PF6 - and SO3CF3 - Selected from.

[0023] In some embodiments, the compound is selected from the following: [ka] [ka] [ka] [ka] [ka]

[0024] In another embodiment, Cathode material and, Anode material and, The cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, wherein the first polymer matrix is ​​configured to prevent or minimize substantial diffusion of the cathode material. An energy storage device is provided in which the anode material comprises one or more of the phenazine compounds described herein, covalently bonded to or confined within a second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the anode material.

[0025] In another embodiment, A first cell containing anode material, A second cell containing cathode material, It includes a porous separator that separates the first cell from the second cell, The anode material comprises one or more of the phenazine compounds described herein. An energy storage device is provided in which the cathode material contains viologen.

[0026] In some embodiments, the energy storage device further comprises a solvent and an electrolyte containing a metal salt or ammonium salt. In some embodiments, the separator includes an ion exchange membrane or a size exclusion membrane. In some embodiments, the energy storage device is a battery. [Brief explanation of the drawing]

[0027] [Figure 1] Figure 1 shows the UV cycle durability (3 hours on / 1 hour off) of devices A and B described in the examples. [Figure 2] Figure 2 shows the 85°C cycle endurance (3 hours on / 1 hour off) of devices A and B described in the examples. [Modes for carrying out the invention]

[0028] Various embodiments are described below. It should be noted that no particular embodiment is intended to be an exhaustive description or a limitation to a broader set of embodiments described herein. An embodiment described in conjunction with a particular embodiment is not necessarily limited to that embodiment and may be carried out in any other embodiment.

[0029] As used herein, "about" is to be understood by those skilled in the art and may vary to some extent depending on the context in which it is used. Where there is any use of terminology that is unclear to those skilled in the art, "about" should be understood to mean up to 10 percent plus or minus 10 percent of a given period, taking into account the context in which it is used.

[0030] The use of the terms “a,” “an,” “the,” and similar referents in the context describing elements (in particular, in the context of the following claims) is to be interpreted as encompassing both singular and plural unless otherwise indicated herein or if it is clearly inconsistent with the context. The descriptions of ranges of values ​​herein are intended only as a concise way of referring individually to each individual value within that range unless otherwise indicated herein, and each individual value is incorporated herein as if it were described separately herein. Unless otherwise indicated herein or if it is clearly inconsistent with the context otherwise, all methods described herein may be carried out in any suitable order. All examples or illustrative phrases provided herein (e.g., the use of “such as”) are intended only to better illustrate embodiments and do not limit the claims unless otherwise indicated. No phrase herein should be interpreted as indicating that any non-claimed element is essential.

[0031] Generally, "substitution" refers to an alkyl group, alkenyl group, aryl group, or ether group in which one or more bonds with a hydrogen atom contained therein are replaced by a non-hydrogen or non-carbon bond, as defined below (e.g., alkyl group). Substitutions also include groups in which one or more bonds with a carbon or hydrogen atom are replaced by one or more bonds with a heteroatom, including double or triple bonds. Thus, unless otherwise specified, a substituent is substituted by one or more substituents. In some embodiments, a substituent is substituted by one, two, three, four, five, or six substituents. Examples of substituents include halogens (i.e., F, Cl, Br, and I), hydroxyl, alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups, aralkyloxy groups, heterocyclyloxy groups, and heterocyclylalkoxy groups, carbonyl (oxo), carboxyl, esters, urethanes, oximes, hydroxylamines, alkoxyamines, aralkoxyamines, thiols, sulfides, sulfoxides, sulfones, sulfonyls, sulfonamides, amines, N-oxides, hydrazines, hydrazides, hydrazones, azides, amides, ureas, amidines, guanidines, enamines, imides, isocyanates, isothiocyanates, cyanates, thiocyanates, imines, nitro groups, nitriles (i.e., CN), and the like.

[0032] As used herein, the “alkyl” group includes linear and branched alkyl groups having 1 to about 20 carbon atoms, typically 1 to 12 carbon atoms, or in some embodiments 1 to 8 carbon atoms. As used herein, “alkyl group” includes cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted. Alkyl groups may be substituted once or more times. Alkyl groups may be substituted two or more times. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl, and 1-cyclopentyl-4-methylpentyl. Typical substituted alkyl groups may be substituted once or more times with, for example, amino, ammonium, thio, hydroxy, cyano, alkoxy, and / or halo groups such as F, Cl, Br, and I groups. As used herein, the term haloalkyl refers to an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a perhaloalkyl group.

[0033] Cycloalkyl groups are cyclic alkyl groups, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, cycloalkyl groups have 3 to 8 ring components, while in other embodiments, the number of ring carbon atoms ranges from 3 to 5, 6, or 7. Cycloalkyl groups can be substituted or unsubstituted. Cycloalkyl groups further include polycyclic cycloalkyl groups, including but not limited to norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and calenyl groups, as well as fused rings, including but not limited to dekalinyl and similar groups. Cycloalkyl groups also include rings substituted with linear or branched alkyl groups as defined above. Typical substituted cycloalkyl groups are not limited to, but may include, for example, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups, or monosubstituted, disubstituted, or trisubstituted norbornyl or cycloheptyl groups, which can be substituted with alkyl, alkoxy, amino, thio, hydroxyl, cyano, and / or halo groups.

[0034] Alkenyl groups are linear, branched, or cyclic alkyl groups having 2 to about 20 carbon atoms and containing at least one double bond. In some embodiments, alkenyl groups have 1 to 12 carbon atoms, or typically 1 to 8 carbon atoms. Alkenyl groups can be substituted or unsubstituted. Among the many types of alkenyl groups are, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups. Alkenyl groups can be substituted, as can alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with two attachment sites, include, but are not limited to, CH-CH=CH2, C=CH2, or C=CHCH3.

[0035] As used herein, an "aryl" or "aromatic" group is a cyclic aromatic hydrocarbon that does not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic systems. Thus, aryl groups include, but are not limited to, phenyl, azlenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenantrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentarenyl, and naphthyl groups. Aryl groups having one or more alkyl groups may also be called alkaryl groups. In some embodiments, an aryl group has 6 to 14 carbon atoms in the ring portion of the group, and in others, 6 to 12 or 6 to 10 carbon atoms. The term "aryl group" includes groups containing fused rings, such as fused aromatic aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and similar groups). The aryl group can be substituted or unsubstituted.

[0036] A heterocyclic or heterocycle refers to a compound, including monocyclic, bicyclic, and polycyclic rings containing three or more ring members, encompassing both aromatic and non-aromatic cyclic compounds, where one or more of the ring members are heteroatoms such as, but not limited to, N, O, and S. Examples of heterocyclic groups include unsaturated 3-8 membered rings containing 1-4 nitrogen atoms (pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl, dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridadinyl), triazolyl (e.g., 4H-1,2,4-triazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, etc.), and tetrazolyl (e.g., 1H-tetrazolyl, 2H-tetrazolyl, etc.). (but not limited to these), saturated 3-8 membered rings containing 1-4 nitrogen atoms (such as pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl, etc., but not limited to these), condensed unsaturated heterocyclic groups containing 1-4 nitrogen atoms (such as indolyl, isoindolyl, indolinyl, indolidinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl, etc., but not limited to these), 1- Unsaturated 3-8 membered rings containing 2 oxygen atoms and 1-3 nitrogen atoms (oxazolyl, isoxazolyl, oxadiazolyl (e.g., 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, etc.), but not limited to these), saturated 3-8 membered rings containing 1-2 oxygen atoms and 1-3 nitrogen atoms (e.g., morpholinyl, etc.), unsaturated condensed heterocyclic groups containing 1-2 oxygen atoms and 1-3 nitrogen atoms (e.g., benzoxazolyl, benzoxadiazolyl, benzoxazinyl (e.g., 2H-1,4-benzoxazinyl, etc.)), unsaturated 3-8 membered rings containing 1-3 sulfur atoms and 1-3 nitrogen atoms (thiazolyl, isothiazolyl, thiadiazolyl (e.g., 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,These include, but are not limited to, 5-thiadiazolyl, saturated 3-8 membered rings containing 1-2 sulfur atoms and 1-3 nitrogen atoms (such as thiazolodinyl, but are not limited to), saturated and unsaturated 3-8 membered rings containing 1-2 sulfur atoms (such as thienyl, dihydrodithinyl, dihydrodithionyl, tetrahydrothiophene, tetrahydrothiopyran, but are not limited to), and unsaturated condensed heterocycles containing 1-2 sulfur atoms and 1-3 nitrogen atoms (such as benzothiazolyl, benzothiadiazolyl, benzothiadinyl (e.g., 2H-1,4-benzothiadinyl, etc.), dihydrobenzothiadinyl (e.g., 2H-3,4-dihydrobenzothiadinyl, etc.)). Heterocyclic groups also include, but are not limited to, unsaturated 3- to 8-membered rings containing an oxygen atom (such as furyl, but not limited thereto), unsaturated condensed heterocyclic rings containing 1-2 oxygen atoms (such as benzodioxolyl (e.g., 1,3-benzodioxoyl, etc.)), unsaturated 3- to 8-membered rings containing an oxygen atom and 1-2 sulfur atoms (such as dihydrooxathinyl, but not limited thereto), saturated 3- to 8-membered rings containing 1-2 oxygen atoms and 1-2 sulfur atoms (such as 1,4-oxathiane), unsaturated condensed rings containing 1-2 sulfur atoms (such as benzothienyl, benzodithinyl, etc.), and unsaturated condensed heterocyclic rings containing an oxygen atom and 1-2 oxygen atoms (such as benzoxathinyl, etc.). Heterocyclic groups also include those described above, in which one or more sulfur atoms of the ring are double-bonded to one or two oxygen atoms (sulfoxides and sulfones). For example, heterocyclic groups include tetrahydrothiophene oxide and tetrahydrothiophene 1,1-dioxide. Typical heterocyclic groups contain 5 or 6 ring members. Therefore, for example, heterocyclic groups include morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2This includes 4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl, thiomorpholinyl (where the S atom of thiomorpholinyl is bonded to one or more O atoms), pyrrolyl, pyridinyl homopiperazinyl, oxazolidine-2-onyl, pyrrolidine-2-onyl, oxazolyl, quinuclidinyl, thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl. Heterocyclic groups or heterocycles may be substituted.

[0037] A heteroaryl group is an aromatic ring compound containing five or more ring members, one or more of which are heteroatoms such as N, O, and S, but not limited to these. Heteroaryl groups include pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridadinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, dibenzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimimidazolyl, and imidazopyridinyl (azabenzimidyl) groups. Heteroaryl groups include, but are not limited to, groups such as dazolyl, pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, prinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl. Heteroaryl groups include fused ring compounds in which all rings are aromatic (such as indolyl groups) and fused ring compounds in which only one of the rings is aromatic (such as 2,3-dihydroindolyl groups). The term "heteroaryl group" includes fused ring compounds, but does not include heteroaryl groups that have other groups attached to one of the ring members, such as alkyl groups. Rather, heteroaryl groups with such substitutions are called "substituted heteroaryl groups." Typical substituted heteroaryl groups can be substituted once or multiple times with various substituents, such as those listed above.

[0038] As used herein, the prefix "halo" refers to a halogen (i.e., F, Cl, Br, or I) bonded to a group modified by the "halo" prefix. For example, a haloaryl is an aryl halide group.

[0039] Groups described herein that have two or more attachment sites within the compounds of this technology (i.e., divalent, trivalent, or polyvalent) are indicated by the use of the suffix "ene". For example, a divalent alkyl group is an alkylene group, a divalent aryl group is an arylene group, a divalent heteroaryl group is a divalent heteroarylene group, and so on.

[0040] This disclosure relates to electrochromic devices incorporating specific phenazine compounds as anodic redox species. As described below, the phenazine compounds disclosed herein are substituted with at least one sterically hindered group (e.g., a tertiary butyl group). As shown in the examples, the phenazine compounds described herein are thermally stable and have improved weather resistance, such as electrical cycling under UV exposure (about 390 nm or higher). The phenazines described herein are electrochromic.

[0041] More broadly, energy storage devices and / or electrochromic memory devices are disclosed herein that include cathode material and anode material such that the device maintains an activated (i.e., dark) state in an open circuit for an extended period when the cathode material and anode material are activated. When the terms cathode material and anode material are used herein, at least one of them is electrochromic. The cathode material / part may be associated with a first conductive substrate or isolated within a polymer matrix, and the anode material / part may be associated with a second conductive substrate or isolated within a polymer matrix. For example, the anode material may be covalently crosslinked and coated onto a second conductive substrate, and the cathode material may be covalently crosslinked and coated onto the surface of a first conductive substrate. Coating the anode material and cathode material to a substrate prevents the anode material and cathode material from moving within the device, thus potentially maintaining an activated state indefinitely.

[0042] As described above, the anode or cathode material may also be part of the polymer matrix, covalently bonded to the polymer. This can be achieved by the presence of functional groups on the anode or cathode material that react with the polymer or the monomers constituting the polymer. For example, if the anode or cathode material contains a hydroxyl group, it may be bonded to the polymer matrix by a condensation reaction or react with isocyanate functionalities to form a polyurethane polymer matrix. Amines may also react with isocyanate functionalities to form a urea-biuret bond. Other crosslinked polymer matrices can be expected to be formed by using polyfunctional epoxy or polymer in combination with a curing agent such as an amine, alcohol or anhydride, or by monopolymerization with a base or acid catalyst.

[0043] A typical solution-phase electrochromic device contains at least one anode (easily oxidizable) material or species, at least one cathode (reducible) material or species, and a solvent. When a sufficient potential is applied to the solution-phase electrochromic device (i.e., activated), a typical solution-phase device undergoes a color change (i.e., a dark or low-transparency state). Since the anode and cathode materials can freely diffuse through the solvent while in the activated state, the electrochromic device self-extinguishes when the charging potential is removed. It has been found that isolating the anode material on the surface of a conductive substrate while isolating the cathode material on the surface of a second conductive substrate results in an electrochromic device configured to maintain a charged state, i.e., an activated state, for a longer period of time, compared to a typical solution-phase electrochromic device, as long as the electrochromic anode and cathode films are separated by an ionic conductive electrolyte.

[0044] The electrochromic device described herein may include at least one chamber defined by a first substrate having a first conductive surface, a second substrate having a second conductive surface, and a sealing member that joins the first substrate to the second substrate in contact with the sealing member, the first and second conductive surfaces. Regarding the surface constraints of the anode and cathode materials, the anode material may be isolated on one conductive surface, and the cathode material may be isolated on the other conductive surface. An electrolyte is disposed within the chamber between the anode and cathode layers. The first and second substrates may be offset from each other to allow electrical contact between the first and second conductive surfaces, as is well established for other solution-phase electrochromic devices.

[0045] In one embodiment, an energy storage device or memory device is provided. The energy storage device or memory device may include a cathode material and an anode material. The cathode material may be viologen, and the anode material may be phenazine as described herein.

[0046] In some embodiments, the anode material includes a phenazine compound represented below: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 Each of these is independently H, F, Cl, Br, I, CF3, CN, OR 11 , SR 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups among them may bond to form a monocyclic, polycyclic, or heterocyclic group. Each R 11 is independently H or alkyl, R 5 and R 10 They are independent, (i) -L1-A-L2-OR 14 Represented by, Each L1 is independently a C1-C8 alkylene group. Each L2 is independently a C1-C8 alkylene group. Each R 14 is either H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is either alkyl or alkylhydroxy, or (ii) -L3-OR 16 Represented by, Each L3 is independently a C1-C8 alkylene group. Each R 16 is either H or alkyl, R 2 , R3 , R 7 , and R 8 At least one of them is a sterically hindered group.

[0047] The sterically hindered group can be selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl. The sterically hindered group may also be an alkyl group containing an isopropyl moiety. In some embodiments, the sterically hindered group is not a methyl group.

[0048] In some embodiments, R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 Each of these is independently H. In some embodiments, R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 Each of these is independently H.

[0049] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of them is independently a C2-C8 alkyl group. In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of these is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of these is independently isopropyl, neopentyl, or tertiary butyl.

[0050] In some embodiments, R 2 and R7 , or R 2 and R 8 Each of these is independently a C2-C8 alkyl group. In some embodiments, R 2 and R 7 , or R 2 and R 8 Each of these is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 2 and R 7 , or R 2 and R 8 Each of these is independently isopropyl, neopentyl, or tertiary butyl.

[0051] In some embodiments, R 3 and R 8 , or R 3 and R 7 Each of these is independently a C2-C8 alkyl group. In some embodiments, R 3 and R 8 , or R 3 and R 7 Each of these is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. In some embodiments, R 3 and R 8 , or R 3 and R 7 Each of these is independently isopropyl, neopentyl, or tertiary butyl.

[0052] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of them is independently an arrow. In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of them is independently phenyl.

[0053] In some embodiments, R 2 and R 7 , or R 2 and R 8 Each is an independent aryl. In some embodiments, R 2 and R 7 Each of these is independently a phenyl compound.

[0054] In some embodiments, R 3 and R 8 , or R 3 and R 7 Each is an independent aryl. In some embodiments, R 3 and R 8 , or R 3 and R 7 Each of them is independently a phenyl compound.

[0055] In some embodiments, R 5 and R 10 At least one of them independently -L1-A-L2-OR 14 Represented by, Each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 These are C1-C8 alkyl or C1-C8 alkylhydroxyl compounds.

[0056] In some embodiments, Each L1 is independently a C2 or C4 alkylene group. Each L2 is independently a C3 alkylene group. Each R 14 H is, A is -N(R 15)2 + - is an ammonium group represented by Each R 15 These are C1 alkyl or C2 alkylhydroxyl.

[0057] In some embodiments, R 5 and R 10 At least one of these is independently represented as follows: [ka] n is 1, 2, 3, 4, 5, 6, 7, or 8. x is 1, 2, 3, 4, 5, 6, 7, or 8. Each R 15 These are independently C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0058] In some embodiments, n is 2 or 4. x is 3, Each R 15 These are independently C1 alkyl or C2 alkylhydroxyl.

[0059] In some embodiments, R 5 and R 10 At least one of them independently -L3-OR 16 Represented by, Each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each R 16 is either H or alkyl.

[0060] In some embodiments, each L3 is independently a C4 or C6 alkylene group. Each R 16 H is H.

[0061] In some embodiments, R 5 and R 10 At least one of these is independently represented as follows: [ka] y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0062] In some embodiments, y is 3 or 6.

[0063] In some embodiments, the compound is F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , BAr4 - or an ammonium salt having an anion comprising a mixture of the anion thereof, where Ar is an aryl group or a fluorinated aryl group. In some embodiments, the anion is PF6 - , SO3CF3 - , and a mixture of those anions are selected.

[0064] According to various embodiments of this specification, the phenazine compounds disclosed herein may be any one of the following compounds. As described above, some of the disclosed phenazines have at least one net positive charge electronically balanced by an anion (not shown). The anion may be any of the various anions described above. [ka] [ka] [ka] [ka]

[0065] In another embodiment, the electrochromic device includes an anode material coated on the surface of a first conductive substrate and covalently crosslinked, and a cathode material coated on the surface of a second conductive substrate and covalently crosslinked. The electrochromic device exhibits a high-transmittance state when short-circuited and a low-transmittance state when a potential is applied, with the high-transmittance state being at least four times greater than the low-transmittance state. The electrochromic device is configured to maintain a transmittance of no more than 5% of the low-transmittance state for at least 8 hours at 20°C in an open circuit after a potential sufficient to reach the low-transmittance state has been applied. In some embodiments, the electrochromic device is configured to maintain a transmittance of no more than 5% of the low-transmittance state for at least 8, 10, 15, 20, 24, or 48 hours at 20°C in an open circuit after a potential sufficient to reach the low-transmittance state has been applied. In some embodiments, the device is configured to maintain a transmittance of no more than 10% of the low-transmittance state for at least 2, 3, 4, or 5 days at 20°C in an open circuit after a potential sufficient to reach the low-transmittance state has been applied. In some embodiments, the device is configured to maintain a transmittance of less than 10% of the low transmittance state for 8 hours to 10 days in an open circuit at 20°C after applying a potential sufficient to reach the low transmittance state. The low transmittance state may range from about 0.001% to about 30%. The high transmittance state ranges from about 50% to about 95%. In some embodiments, after 4000 cycles from the high transmittance state to the low transmittance state, the high transmittance value does not change by more than 5% from the initial high transmittance value. As used herein, the initial high transmittance value is the state of the device before applying a potential after the device is manufactured. In some embodiments, after 4000 cycles from the high transmittance state to the low transmittance state, the low transmittance value does not change by more than 5% from the initial low transmittance value. As used herein, the initial low transmittance value is the low transmittance value achieved by the first charge of the device with full voltage applied.

[0066] In any of the above embodiments, the cathode material may be a viologen, a low-dimerized viologen, or a non-dimerized viologen. The term low-dimerized viologen applies to some viologens that exhibit dimerization properties to a lower degree than dimerized viologens. The viologen material may be sequestered within the polymer matrix by being physically confined internally, or the viologen material may be functionalized to accept polymerization or reaction with the polymer so as to be covalently bonded to the polymer. Exemplary viologens include, but are not limited to, methyl viologen, octyl viologen, benzyl viologen, polymerized viologen, and viologens described in U.S. Patents 4,902,108, 6,188,505, 5,998,617, 10,464,900, and 6,710,906. Other viologens may include the viologen of formula (I), (III), or (IV). Equation (I): [ka] In formula I, R 1 and R 2 These are individually alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl, and R 4 , R 6 , R 8 and R 10 Each of these is individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 3 , R 5 , R 7 , and R 9 R is individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and X is an anion. However, formula (I) is R 3 and R 5 , or R 7 and R 9 , or R 3 , R 5 , R 7 , and R 9 These may be defined individually as secondary alkyl, tertiary alkyl, or aryl. Formula (III): [ka] In formula (III), R 1 and R 2 These are individually alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl, and R 4 , R 6 , R 8 , R 10 Each of these is H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 3 , R 5 , R 7 , and R 9 Each of these is H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 19 (CH2) n’ Or it is an allerene, n' is 1 to 12, X is an anion, R 3 and R 5 , or R 7 and R 9 These are individually secondary alkyl, tertiary alkyl, or aryl compounds. Formula (IV): [ka] In formula (IV), R 1 and R 1’ These are individually alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl, and R 4 , R 6 , R 8 , R 10 , R 4’ , R 6’ , R 8’ , and R 10’ Each of these is individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 7 , R 9 , R 7’ , and R 9’Each of these is individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 19 (CH2) n’ Or it is an allerene, where n' is 1 to 12, X is an anion, and R 3 , R 5 , R 3’ , and R 5’ However, individually, they may be secondary alkyl, tertiary alkyl, or aryl, or R 7 , R 9 , R 7’ , and R 9’ These are individually secondary alkyl, tertiary alkyl, or aryl. For any of the viologens described, the counterion (anion) may be a halide, borate, fluoroborate, tetraarylborate, hexafluorometal or metalloid, sulfate, sulfonate, sulfonamide, carboxylate, perchlorate, tetrachloroferrate, etc., or a mixture of two or more of these. Exemplary counterions / anions include, but are not limited to, F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , or BAr4 - This includes a group where Ar is an aryl, fluorinated aryl, or bis(trifluoromethyl)aryl group. In some embodiments, X is a tetrafluoroborate or bis(trifluoromethylsulfonyl)imide anion.

[0067] In any of the above embodiments, the anode material may be one or more of the phenazine compounds described herein, covalently bonded to or confined within the second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the activated anode material. With respect to the viologen, the anode material may be sequestered within the polymer matrix by being physically confined inside, or the anode material may be functionalized to be polymerized or to be receptive to reacting with the polymer so as to be covalently bonded with the polymer.

[0068] Further examples of anode and cathode materials can be found in U.S. Patents 4,902,108, 5,294,376, 5,998,617, 6,193,912, 10,971,718, and 8,228,590.

[0069] If the device contains an electrolyte, the electrolyte may contain a solvent and a salt. The salt may be a metal salt or an ammonium salt. Exemplary solvents used in electrolytes may include, but are not limited to, 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraglyceride, and other polyethers; alcohols such as ethoxyethanol; nitriles such as acetonitrile, glutaronitrile, 3-hydroxypropionitrile, and 2-methylglutaronitrile; ketones including 2-acetylbutyrolactone and cyclopentanone; cyclic esters including β-propiolactone, γ-butyrolactone, and γ-valerolactone; propylene carbonate (PC), ethylene carbonate, and homogeneous mixtures thereof. While specific solvents are disclosed in relation to electrolytes, a number of other solvents known to those skilled in the art who have had prior disclosures are also intended for use. Exemplary salts may include, but are not limited to, Li + na + , K + NR'4 +Examples include, but are not limited to, metals or ammonium salts, where each R' is individually F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , or BAr4 - The anion is H, alkyl, or cycloalkyl, where Ar is an aryl, or aryl fluoride group such as C6H5, 3,5-(CF3)2C6H3]4, or C6F5, etc. Further examples of polymer electrolyte materials used in electrochromic devices can be found in U.S. Patents 6,635,194 and 5,940,201.

[0070] Regarding the substrate and the conductive coating on the substrate, those commonly used in solution-based electrochromic devices may be used. For example, one or both substrates may be glass, metal, plastic, or ceramic. The conductive coating on one or more substrates may be transparent or opaque depending on the intended use of the device. For example, if the device is a window, both coatings should be substantially transparent, and if the device is a mirror, at least one coating should be transparent. Exemplarily, transparent conductive materials include, but are not limited to, fluorine-doped tin oxide (FTO), indium tin oxide (ITO), doped zinc oxide, indium zinc oxide, metal oxide / Ag / metal oxide, silver nanowire coating, carbon nanotube, graphene coating, wire grid, and conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT). Non-transparent conductive coatings include metal coatings such as rhodium, chromium, nickel, silver, gold, and other metals, or mixtures of any two or more of them.

[0071] Therefore, the present invention generally described can be more easily understood by referring to the following examples, which are provided for illustration purposes and are not intended to limit the present invention.

Examples

[0072] Examples

[0073] Example 1. 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium)hexafluorophosphate Synthesis of.

[0074] The four-step synthesis of the title compound is as follows. Step 1: 2,7(8)-di-tert-butyl-5,10-dihydrophenazine (as a mixture of two isomers)

Chemical formula

[0075] Step 1: 400.0 g of 4-(tert-butyl)benzene-1,2-diamine, 992 g of 4-(tert-butyl)benzene-1,2-diol, and 1330 mL of ethylene glycol were added to a 5 L three-neck round-bottom flask equipped with a Dean-Stark condenser, a mechanical stirrer, and a thermometer. The mixture was heated to 203 °C for one week under a nitrogen atmosphere. The reaction mixture was then cooled to 60 °C. To prevent oxidation, the solids were filtered under inert conditions. The solids were then washed with a 1:1 mixture of acetone and water (4 L). The solids were recrystallized by first partially dissolving them in 1 L of acetone, and then an aqueous sodium dithionite solution was added (160 g dissolved in 2 L of water). Finally, the solution was cooled to room temperature and the solids were filtered under inert conditions. Removal of the solvent in vacuo gave 516 g (72% yield) of 2,7-di-tert-butyl-5,10-dihydrophenazine. GC analysis showed a 99.8% pure product.

[0076] Step 2: A 12-liter round-bottom flask was filled with 1,4-dibromobutane (2260 g) and acetone (6 L). The flask was cooled to 5-7°C. Dimethylaminopropanol (1200 g) was slowly added using an addition funnel. The reaction was slightly exothermic. After the addition was complete, the temperature was raised to room temperature. After stirring at room temperature for 48 hours, the product precipitated as white crystals. The solid product was filtered and washed with acetone. Vacuum drying yielded 3112 g of the desired product (93% yield).

[0077] Step 3: 240 g of 2,7-di-tert-butyl-5,10-dihydrophenazine, 1154 g of 4-bromo-N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium bromide, 280 g of sodium dithionite, 375 g of sodium carbonate, 30 g of methyltributylammonium chloride, 30 mL of water, and 7400 mL of acetonitrile were added to a 12 L round-bottom flask. The mixture was heated under a nitrogen atmosphere under reflux for 48 hours, and HPLC analysis showed that dihydrophenazine was not present. Then, 3 L of acetonitrile was removed by distillation, and the reaction mixture was allowed to cool to room temperature. The reaction solids were then filtered and washed with 2.5 L of acetone. The solids were redissolved in 1.3 L of water, heated, and residual acetone was removed by distillation at 70°C. 2 L of ethanol was added, and the reaction mixture was allowed to cool to room temperature. The solids were filtered and washed with ethanol. The solid was discarded, and the filtrate containing the product was concentrated into an oily substance under vacuum. The oily substance was added to 6 L of warm acetone. After cooling, the filtrate was decanted, and the rubbery solid was washed with additional acetone. The rubbery solid was, 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) It was a bromide, which was used directly to prepare the PF6 salt. The product was 99% pure by HPLC and mass ES analysis. Step 4: 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) Synthesis of hexafluorophosphates.

[0078] First metathesis: 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium)The rubbery solid of bromide was dissolved in 900 mL of water and 100 mL of triethylamine mixture by heating to 50°C. 2500 mL of 30% NH4PF6 aqueous solution was added, and the reaction was stirred at 50°C for 5 hours. After cooling the reaction, 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) Hexafluorophosphate precipitated as a gray solid in 720 g of wet solids.

[0079] A second metathesis was repeated by dissolving the solid in 350 mL of acetonitrile, 1000 mL of water, 150 mL of triethylamine, and 1000 mL of ethanol. The reaction mixture was heated to 65°C and 1700 mL of 30% NH4PF6 solution was added. After continuing to heat for 3 hours, 1000 mL of water was added. 150 mL of acetonitrile was removed by distillation and the reaction mixture was cooled to room temperature. Upon cooling, the product solidified. The filtrate was decanted and the product was washed with 3 L of cold water to obtain a rubbery solid. The solid was dissolved in 1000 mL of acetonitrile. Acetonitrile and residual water were completely removed under vacuum to obtain a brown concentrate. To the brown concentrate, a mixture of 4000 mL of ethanol, 100 mL of triethylamine, and 10 mL of anhydrous hydrazine was added. After continuing to heat at 60°C for 15 minutes, the reaction mixture was cooled to 40°C and 2000 mL of hexane was added. The reaction mixture was cooled to room temperature, then cooled to 0–5°C for 4 hours. The solid was filtered under inert conditions and washed with 1000 mL of cold ethanol, followed by a 1:1 mixture of ethanol and hexane in 1000 mL of water. The solid was vacuum-dried to obtain 494 g (64% yield) of an off-white solid. The product was 99.5% pure by HPLC and mass spectrometry.

[0080] Example 2. 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) Triflat synthesis:

[0081] 50g 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) Bromide was dissolved in 85 mL of warm water, and 250 mL of 30% sodium triflate was added. The reaction mixture was heated at 60°C for 4 hours. 200 mL of water was added, and the mixture was then cooled to room temperature. The product was filtered and washed with 300 mL of water under inert conditions.

[0082] The second metathesis was carried out by dissolving the above solid in 150 mL of warm water. 20 mL of triethylamine was added. The reaction mixture was stirred at 50 °C for 5 hours. The reaction mixture was cooled, filtered, and vacuum dried to obtain 50 g (yield 82%) of 4,4'-(2,7-di-tert-butylphenazine-5,10-diyl)bis(N-(3-hydroxypropyl)-N,N-dimethylbutane-1-aminium) triflate as a white solid. The product was 99.9% pure by HPLC and mass spectrometry.

[0083] Example 3. Formulation and process for preparing a phenazine-based device

[0084] In this example, Device A was fabricated with the following compound: [Chemical formula]

[0085] In this example, Device B was fabricated with the following compound: [Chemical formula]

[0086] Device A was prepared by dissolving 0.3518 grams of bis N,N'-(6-hydroxyhexyl)viologen bis[bistrifluoromethanesulfonylimide] (NTF), 0.0149 grams of octamethylbis(6-hydroxyhexyl)ferrocenium bis(tetrafluoroborate), 0.0006 grams of surfactant (TEGO Glide 410), and 0.1433 grams of HDT-isocyanurate (Desmodur N3300, Covestro) in a 3-gram solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35 wt% PC, 65 wt% MPN) with 100 ppm of dibutyltin diacetate (DBTDA) catalyst added, and coating an indium tin oxide (ITO)-coated 3-inch × 3-inch glass sheet (2.2 mm thick). A 16th Meyer rod was used to coat the mixture directly onto the ITO coating to control the thickness.

[0087] For device A, a second piece of 3-inch x 3-inch ITO-coated glass (2.2 mm thick) was coated with a solution prepared by dissolving 0.3969 grams of 5,10-bis(n-butyl-N,N-dimethylammonium n-propanol)phenazine triflate, 0.0166 grams of octamethylbis(6-hydroxyhexyl)ferrocene, 0.0006 grams of surfactant (TEGO Glide 410), and 0.1866 grams of HDT-isocyanurate (Desmodur N3300, Covestro) in a 3-gram solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35 wt% PC, 65 wt% MPN) with 100 ppm DBTDA catalyst. The second film was prepared by coating the solution with an 8-gauge Meyer rod to control its thickness.

[0088] Device B was prepared by coating a 3-inch x 3-inch glass piece (2.2 mm thick) coated with indium tin oxide (ITO) using a solution prepared by dissolving 0.3588 g of bis(6-hydroxyhexyl) viologenbis[bistrifluoromethanesulfonyliimide] (NTF), 0.0149 g of octamethyldihexanolferoceniumbis(tetrafluoroborate), 0.0006 g of surfactant (TEGO Glide 410), and 0.1433 g of HDT-isocyanurate (Desmodur N3300, Covestro) in 3 g of a solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN) with 100 ppm of dibutyltin diacetic acid (DBTDA) catalyst. The film was prepared by coating the solution with a No. 16 Meyer rod to control the thickness.

[0089] Furthermore, for device B, the composition is 0.4112 grams of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenadine-5(10H)-yl)-N,N-dimethylbutane-1-aminium bis(hexafluorophosphate), 0.0152 grams of octamethylbis(6-hydroxyhexyl)ferrocene, 0.0006 grams of surfactant (TEGO Glide 410), and 0.1706 grams of HDT-isocyanurate (Desmodur A second film was formed by coating a second piece of 3-inch x 3-inch ITO-coated glass (2.2 mm thick) with a solution prepared by dissolving N3300 (Covestro) in 3 grams of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN) with 100 ppm DBTA. This second film was prepared using an 8-gauge Meyer rod.

[0090] The above films were cured overnight in a 60°C oven under a nitrogen atmosphere. Once the films had cured, the edges of the films (less than 1 cm) were removed to accommodate the epoxy seal and electrical contacts to the ITO. The first and second films on each ITO-coated glass substrate were positioned in a spatially separated relationship facing each other, with the epoxy seal placed around the periphery and cured to form a cell, leaving an offset for mounting the electrical contacts. The distance between the two substrates was approximately 135 micrometers. The resulting cells were filled with a solution of 0.1 moles of tetraethylammonium bis-trifluoromethanesulfone imidate (TEANTF) and a crosslinkable polymer matrix precursor in PC to form a gel electrolyte.

[0091] Devices A and B, each containing two different anodic compounds, were subjected to various durability tests.

[0092] Figure 1 shows the results of the UV cycle endurance test for devices A and B. The devices were xenon lamp weather meters (0.55 W / m² at 340 nm). 2Devices A and B were exposed to an Atlas Weather-Ometer for 4000 hours. Devices A and B were tested behind a light attenuator fabricated by laminating two Kuraray UV extra protect PVB films (Trosifol®) and one 3M® Ultraclear Solar IR reflective film between two sheets of soda-lime glass (one 1.1 mm thick and one 2.2 mm thick). The cycle profiles for both devices consisted of 3 hours in the dark and 1 hour in the clear state. Device A was cycled between the clear state (0 volts) and the completely dark state (0.8 volts), while Device B was cycled between the clear state (0 volts) and the completely dark state (0.7 volts). After 4000 hours, the delta-E of Device B in UV cycling was only 13.9, while Device A showed significant color change with a delta-E of 30.

[0093] Device B, fabricated with a phenazine compound containing a tert-butyl group, showed a significant improvement in UC cycle durability, as shown in Figure 1.

[0094] Figure 2 shows the results of the 85°C cycle endurance test for devices A and B. The cycle profile for both devices consisted of 3 hours in darkness and 1 hour in clear conditions. Device A was cycled between clear (0 volts) and completely dark (0.8 volts), while device B was cycled between clear (0 volts) and completely dark (0.7 volts).

[0095] Article 1 Compounds represented by the following: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9Each of these is independently H, F, Cl, Br, I, CF3, CN, OR 11 , SR 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups among them may bond to form a monocyclic, polycyclic, or heterocyclic group. Each R 11 is independently H or alkyl, R 5 and R 10 They are independent, (i) -L1-A-L2-OR 14 Represented by, Each L1 is independently a C1-C8 alkylene group. Each L2 is independently a C1-C8 alkylene group. Each R 14 is either H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is either alkyl or alkylhydroxy, or (ii) -L3-OR 16 Represented by, Each L3 is independently a C1-C8 alkylene group. Each R 16 is either H or alkyl, R 2 , R 3 , R 7 , and R 8 A compound in which at least one of the groups is a sterically hindered group.

[0096] The compound described in paragraph 1, wherein the sterically hindering group is selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

[0097] Section 3 R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 A compound according to item 1 or 2, wherein each of them is independently H.

[0098] Section 4 R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 A compound according to item 1 or 2, wherein each of them is independently H.

[0099] Section 5 R 2 , R 3 , R 7 , and R 8 A compound according to any one of the items 1 to 4, wherein at least one of them is independently a C2-C8 alkyl group.

[0100] Section 6 R 2 , R 3 , R 7 , and R 8 The compound according to item 5, wherein at least one of them is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0101] Section 7 R 2 , R 3 , R 7 , and R 8 The compound according to item 6, wherein at least one of them is independently isopropyl, neopentyl, or tertiary butyl.

[0102] Section 8 R 2 and R 7 , or R 2 and R 8 A compound according to any one of items 1 to 4, wherein each of the members is independently a C2-C8 alkyl group.

[0103] Section 9 R 2 and R 7 , or R 2 and R 8 The compound according to item 8, wherein each of the elements is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0104] Section 10 R 2 and R 7 , or R 2 and R 8 The compound described in paragraph 9, wherein each of the elements is independently isopropyl, neopentyl, or tertiary butyl.

[0105] Section 11 R 3 and R 8 , or R 3 and R 7 A compound according to any one of the items 1 or 2, wherein each of the members is independently a C2-C8 alkyl group.

[0106] Section 12 R 3 and R 8 , or R 3 and R 7 The compound according to item 11, wherein each of the elements is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0107] Section 13 R 3 and R 8 , or R 3 and R 7 The compound according to item 12, wherein each of the elements is independently isopropyl, neopentyl, or tertiary butyl.

[0108] Section 14 R 2 , R 3 , R 7 and R 8 A compound according to any one of the items 1 to 4, wherein at least one of them is independently an aryl compound.

[0109] Section 15 R 2 , R 3 , R 7 and R 8 The compound described in paragraph 14, wherein at least one of them is independently phenyl.

[0110] Section 16 R 2 and R 7 , or R 2 and R 8 A compound according to any one of the items 1 to 4, wherein each of the elements is independently an aryl compound.

[0111] Section 17 R 2 and R 7 The compound described in paragraph 16, wherein each of the elements is independently phenyl.

[0112] Section 18 R 3 and R 8 , or R 3 and R 7 A compound according to any one of the items 1 or 2, wherein each of the elements is independently an aryl compound.

[0113] Section 19 R 3 and R 8 , or R 3 and R 7 The compound described in paragraph 18, wherein each of the elements is independently phenyl.

[0114] Section 20 R 5 and R 10 At least one of these is independently represented by the following: -L1-A-L2-OR 14 Each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each R 14 is H or alkyl, A is -N(R15 )2 + - is an ammonium group represented by Each R 15 The compound is a C1-C8 alkyl or C1-C8 alkylhydroxyl compound as described in any one of the items 1 to 19.

[0115] Section 21 Each L1 is independently a C2 or C4 alkylene group. Each L2 is independently a C3 alkylene group. Each R 14 H is, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 The compound described in section 20 is a C1 alkyl or C2 alkylhydroxyl compound.

[0116] Section 22 R 5 and R 10 At least one of these is independently represented by the following: [ka] n is 1, 2, 3, 4, 5, 6, 7, or 8. x is 1, 2, 3, 4, 5, 6, 7, or 8. Each R 15 The compound described in any one of the items 1 to 19, wherein is independently a C1-C8 alkyl or a C1-C8 alkylhydroxyl.

[0117] Section 23 n is either 2 or 4. x is 3, Each R 15 The compound described in section 22, wherein is independently a C1 alkyl or a C2 alkylhydroxyl.

[0118] Section 24 R 5 and R 10 At least one of these is independently represented by the following: -L3-OR 16 Each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group. Each R 16 The compound is one of the compounds described in any one of the items 1 to 19, wherein is H or alkyl.

[0119] Section 25 Each L3 is independently a C4 or C6 alkylene group. Each R 16 The compound described in item 24, wherein H is present.

[0120] Section 26 R 5 and R 10 At least one of these is independently represented by the following: [ka] A compound as described in any one of the items 1 to 19, wherein y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0121] Section 27 The compound described in item 26, where y is 3 or 6.

[0122] Section 28 Compound is F - Cl - , Br - , I - BF4 - PF6 - SbF6 - AsF6 - ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - Al(OC(CF3)3)4 - , BAr4 - The compound according to any one of claims 1 to 23, which is an ammonium salt having an anion containing or a mixture of such anions, wherein Ar is an aryl group or a fluorinated aryl group.

[0123] Article 29 Anion is PF6 - and SO3CF3 - A compound selected from the compounds listed in item 28.

[0124] Article 30 The compound described in Article 1, wherein the compound is selected from the following: [ka] [ka] [ka] [ka]

[0125] Paragraph 31 Energy storage device, Cathode material and, Anode material and, The cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, wherein the first polymer matrix is ​​configured to prevent or minimize substantial diffusion of the cathode material. An energy storage device comprising a phenazine compound according to any one of claims 1 to 30, wherein the anode material is covalently bonded to or confined within a second polymer matrix, and the second polymer matrix is ​​configured to prevent or minimize substantial diffusion of the anode material.

[0126] Paragraph 32 Energy storage device, A first cell containing anode material, A second cell containing cathode material, The first cell includes a porous separator that separates the first cell from the second cell, The anode material comprises a phenazine compound according to any one of claims 1 to 30, An energy storage device in which the cathode material contains viologen.

[0127] (Clause 33) The energy storage apparatus according to (Clause 31) or (Clause 32), further comprising a solvent and an electrolyte containing a metal salt or ammonium salt.

[0128] Paragraph 34: An energy storage device according to paragraph 32 or 33, wherein the separator includes an ion exchange membrane or a size exclusion membrane.

[0129] Paragraph 35: An energy storage device as described in any one of paragraphs 31 to 34, wherein the energy storage device is a battery.

[0130] While specific embodiments are described as examples, it should be understood that changes and modifications may be made in accordance with ordinary knowledge in the art without departing from the broader aspects of the art as defined in the following claims.

[0131] The embodiments described herein as illustrative can be adequately implemented without any one or more elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be read broadly and without limitation. Furthermore, the terms and expressions used herein are descriptive and not restrictive, and the use of such terms and expressions is not intended to exclude any equivalents or parts of the illustrated and described features, and it should be recognized that various modifications are possible within the scope of the claimed technology. Also, the phrase “consisting essentially of” should be understood to include the elements specifically listed, as well as additional elements that do not materially affect the fundamental and novel characteristics of the claimed technology. The phrase “consisting of” excludes any elements not specifically identified.

[0132] This disclosure is not limited to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from its spirit and scope. In addition to the methods and compositions enumerated herein, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art from the foregoing. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure is limited only in terms of the entire scope of the appended claims and their equivalents. This disclosure is not limited to any particular methods, reagents, compounds, compositions, or biological systems, and these are naturally subject to change. It will also be understood that the terms used herein are for the sole purpose of describing specific embodiments and are not intended to limit them.

[0133] Furthermore, if any feature or aspect of this disclosure is described from the perspective of the Markush Group, a person skilled in the art will recognize that this disclosure is also described from the perspective of any individual member or subgroup of a member of the Markush Group.

[0134] As will be apparent to those skilled in the art, for all purposes, in particular in terms of providing descriptions, the scope of disclosure herein encompasses all possible subranges and combinations thereof. It will be readily apparent that the enumerated ranges adequately describe and enable the same ranges to be divided into at least 1 / 2, 1 / 3, 1 / 4, 1 / 5, 1 / 10, etc. As a non-limiting example, each range described herein can be readily divided into a lower 1 / 3, a middle 1 / 3, an upper 1 / 3, etc. Also as will be apparent to those skilled in the art, all phrases such as “up to,” “at least,” “greater than,” and “less than” include the numbers enumerated and refer to ranges that can be further divided into subranges as described above. Finally, as will be apparent to those skilled in the art, one range includes individual members.

[0135] All publications, patent applications, issued patents, and other documents referenced herein are incorporated herein by reference in whole, as if each individual publication, patent application, issued patent, or other document were specifically and individually incorporated herein by reference in whole. Definitions contained in the documents incorporated by reference are excluded to the extent that they contradict the definitions in this disclosure.

[0136] Other embodiments are described in the following claims.

Claims

1. A compound represented by the following: 【Chemistry 1】 During the ceremony, R 1 、 R 2 、 R 3 、 R 4 、 R 6 、 R 7 、 R 8 、 and R 9 are each independently H, F, Cl, Br, I, CF 3 、 CN, OR 11 、 SR 11 、 NO 2 、 alkyl, alkoxy, aryl, heteroaryl, amino, or ammonium, Each R 11 is independently H or alkyl, R 5 and R 10 They are independent, -L 1 -AL 2 -OR 14 Represented by, Each L 1 C 1 ~C 8 It is an alkylene group, Each L 2 C 1 ~C 8 It is an alkylene group, Each R 14 is either H or alkyl, A is -N(R 15 ) 2 + - is an ammonium group represented by Each R 15 These are alkyl or alkylhydroxy, R 2 , R 3 , R 7 , and R 8 A compound in which at least one of the groups is a sterically hindered group selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

2. R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 The compound according to claim 1, wherein each of them is H.

3. R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 The compound according to claim 1, wherein each of them is H.

4. R 2 , R 3 , R 7 , and R 8 At least one of them independently, C 2 ~C 8 The compound according to claim 1, wherein it is alkyl.

5. R 2 and R 7 , or R 2 and R 8 Each of them operates independently, C 2 ~C 8 The compound according to claim 1, wherein it is alkyl.

6. R 3 and R 8 , or R 3 and R 7 Each of them operates independently, C 2 ~C 8 The compound according to claim 1, wherein it is alkyl.

7. R 5 and R 10 At least one of them independently, -L 1 -AL 2 -OR 14 Represented by, Each L 1 C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , or C 8 It is an alkylene group, Each L 2 C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , or C 8 It is an alkylene group, Each R 14 is H or alkyl, A is an ammonium group represented by -N(R 15 ), 2 + - and is Each R 15 C 1 ~C 8 Alkyl or C 1 ~C 8 The compound according to claim 1, wherein it is an alkylhydroxyl compound.

8. Each L 1 is independently C 2 or C 4 an alkylene group, Each L 2 C 3 It is an alkylene group, Each R 14 H is, A is -N(R 15 ) 2 + - is an ammonium group represented by Each R 15 C 1 Alkyl or C 2 The compound according to claim 7, wherein it is an alkylhydroxyl compound.

9. R 5 and R 10 At least one of these is independently represented as follows: 【Chemistry 2】 n is 1, 2, 3, 4, 5, 6, 7, or 8. x is 1, 2, 3, 4, 5, 6, 7, or 8. Each R 15 C 1 ~C 8 Alkyl or C 1 ~C 8 The compound according to claim 1, wherein it is an alkylhydroxyl compound.

10. n is either 2 or 4. x is 3, Each R 15 C 1 Alkyl or C 2 The compound according to claim 9, wherein it is an alkylhydroxyl compound.

11. The aforementioned compound is F - Cl - , Br - , I - BF 4 - , PF 6 - SbF 6 - AsF 6 - , 4 - , SO 3 CF 3 - , N(CF 3 SO 2 ) 2 - , C(CF 3 SO 2 ) 3 - , N(SO 2 C 2 F 5 ) 2 - , Al(OC(CF 3 ) 3 ) 4 - , BAR 4 - The compound according to claim 1, which is an ammonium salt having an anion containing or a mixture thereof, wherein Ar is an aryl group or a fluorinated aryl group.

12. The compound according to claim 1, wherein the compound is as follows: 【Chemistry 3-1】 【Chemistry 3-2】 【Chemistry 3-3】 [Chemistry 3-4] [Transformation 3-5]

13. An energy storage device, Cathode material and, Anode material and, The cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, wherein the first polymer matrix is ​​configured to prevent or minimize substantial diffusion of the cathode material. An energy storage device comprising the phenazine compound according to claim 1, wherein the anode material is covalently bonded to or confined within a second polymer matrix, and the second polymer matrix is ​​configured to prevent or minimize substantial diffusion of the anode material.

14. An energy storage device, A first cell containing anode material, A second cell containing cathode material, The first cell includes a porous separator that separates the first cell from the second cell, The anode material comprises the compound described in any one of claims 1 to 12. An energy storage device in which the cathode material contains viologen.

15. The energy storage apparatus according to claim 13, further comprising a solvent and an electrolyte containing a metal salt or ammonium salt.

16. The energy storage device according to claim 14, wherein the porous separator includes an ion exchange membrane or a size exclusion membrane.

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